TWI379853B - Polishing pad - Google Patents
Polishing pad Download PDFInfo
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- TWI379853B TWI379853B TW094136056A TW94136056A TWI379853B TW I379853 B TWI379853 B TW I379853B TW 094136056 A TW094136056 A TW 094136056A TW 94136056 A TW94136056 A TW 94136056A TW I379853 B TWI379853 B TW I379853B
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- polishing pad
- chain extender
- molecular weight
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B7/00—Machines or devices designed for grinding plane surfaces on work, including polishing plane glass surfaces; Accessories therefor
- B24B7/04—Machines or devices designed for grinding plane surfaces on work, including polishing plane glass surfaces; Accessories therefor involving a rotary work-table
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B29/00—Machines or devices for polishing surfaces on work by means of tools made of soft or flexible material with or without the application of solid or liquid polishing agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
- B24D3/001—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as supporting member
- B24D3/002—Flexible supporting members, e.g. paper, woven, plastic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
- B24D3/34—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents characterised by additives enhancing special physical properties, e.g. wear resistance, electric conductivity, self-cleaning properties
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
1379853 九、發明說明: 【發明所屬之技術領域】 • 本發明係關於一種研磨墊。更特定地,其係關於一種具 有由聚胺基歹酸酯或聚胺基甲酸酯-尿素製成之研磨層的 • 研磨墊’具有特別的組合物,並且能夠藉著在高溫、極端 研磨條件下適當地軟化之作為研磨層的外來物質,而減少 要被研磨之表面的損傷。此墊優越地用來研磨半導體晶圓 或類似物的表面。 • 【先前技術】 化學機械研磨(CMP)是吸引許多注意的,為能夠形成極 平坦表面的研磨技術。CMP是藉著讓為研磨顆粒之水性分 散液的於漿’從上方向下流過研磨墊的表面而進行,同時 研磨墊及要被研磨之表面被互相滑動接觸。是假設藉著溫 度變化來抑制研磨墊之彈性係數中的變動,以抑制由研磨 表面之增加溫度、由於研磨表面所產生之磨擦熱導致的研 磨表現變動(參考Us專利6,293,852號及us專利 6’454,634)。然而,當研磨墊之彈性係數在如:高研磨壓 力或高解析度之極端研磨條件下為太高時,在該條件下要 I研磨之表面容易被如:研磨所產生之粉末及包含在於聚 _ 《研磨顆粒凝聚物的外來物質到傷,是難以減少外來物質 對表面的損傷。 移除速率是-個大大影響CMp之生產力的因素。也就 是移除速率可以增加留在研磨塾上齡裂份量而大大改 進至7研磨以使用含微小室㈣丨)之做為CMp研磨塾 105684.doc 1379853 的聚胺基甲酸酯發泡體進行,並且保持淤漿在對此樹脂泡 沫之表面開放的孔(被稱為"孔洞")中。 然而’困難的是自由地控制聚胺基甲酸酯發泡體的發 泡’並且也極難控制在發泡體之整個區域上均勻的孔洞尺 寸及密度。結果是:此導致聚胺基曱酸酯發泡體製成之研 磨墊在品質、移除速率及加工狀態上的差異。 以分散可溶性產物在樹脂中而獲得之研磨墊,已知為能 夠容易藉著發泡來控制孔洞的研磨墊(JP_A 8-500622、JP_ A 2000-33552、JP-A 2000-34416及JP_A 2001-334455)(在 此所用之用語"JP-A”意為”未審查之已出版曰本專利申請 書)。除此之外 ’ JP-A 8-500622 及 JP-A 2000-33552提出含 可溶性產物之研磨墊的有效性。然而,無研究是當這些研 磨墊真正被使用在基材上。 在 JP-A 2000-34416 及 JP-A 2001-334455 中,研究是在研 磨墊的組成材質上,並且觀察到穩定的研磨及移除速率的 改進β然而,更穩定的研磨及淤漿之留持力(reUinability) 和移除速率的進一步改進對真實研磨工作為需要的。 也需要的是進一步改進研磨標的物的平坦性。 【發明内容】 本發明是以上述狀況的觀點所構成。因此,本發明的一 個目的是提供一種研磨墊,其在要被研磨之表面由外來物 質損傷成為問題的極端研磨條件下,很少導致到傷,同時 研磨層之彈性係數趨向於適當地隨溫度上升而下降,該研 磨塾具優良的研磨穩定性、於漿留持力及高移除速率,並 105684.doc 1379853 且在要被研磨之標的物的平坦化上為優越的。 本發明的其他目的及優點會從下列敛述而變得明顯。 根據本發明,首先,本發明的上述目的及優點是以一個 具有由聚胺基甲酸酯或聚胺基甲酸酯-尿素製成之研磨層 的研磨墊所達成,其中 聚胺基甲酸酯或聚胺基曱酸酯-尿素是異氰酸酯終端之 胺基甲酸酯預聚物A及鏈延伸劑B混合物的經固化反應產 物,該鏈延伸劑B在分子中具有兩或多個能夠與異氰酸酯 基團反應的活性含氫基團’並且滿足下列條件"a"及"b": a_該鏈延伸劑由50至100重量%之具有數量平均分子量3〇〇 或更低的鏈延伸劑及50至0重量%之具有數量平均分子 量高於300的鏈延伸劑構成;或 b.該鏈延伸劑由20至100重量%之在分子中具有三或多個 活性含氫基團的鏈延伸劑及80至0重量%之在分子中具 有兩個活性含氫基團的鏈延伸劑構成;並且 該研磨墊在30°C之儲存彈性係數對在60°C之儲存彈性係 數的比率為2至15,並且該研磨墊在30 °C之儲存彈性係數 對在90°C之儲存彈性係數的比率為4至20。 根據本發明’其次’本發明的上述目的及優點是以一個 具有研磨層的研磨墊所達成’其中該研磨層含有分散在由 聚胺基甲酸酯或聚胺基甲酸酯-尿素製成之聚合物基材中 的水溶性顆粒。 較佳具體實施例之詳細敘述 本發明在此後詳細被敘述》 105684.doc 1379853 重要的是:研磨墊首先必須研麼 研磨標的物之要被研磨表面 的大出物,並且很少研磨在砉 隹表面上的凹處,並且在研磨之 末整個表面必須變得平滑。囡 "因此,研磨墊理想的是具有相 對高的硬度,使得研磨塾的表面不變形,並且進入要被研 磨表面上的凹處。同時,當研磨塾具有高硬度時,不佳的 是可改變性(transformability) ’而如研磨所產生之粉末及 齡浆中包含之研磨顆粒凝聚物的外來物質,對要被研磨表 面的損傷(刮傷)增加,因而減少被接受產物的產率。習知 技藝中的研磨塾’固難的是達到高平坦性並且同時抑制刮 傷。本發明之研磨墊的研磨層是以聚胺基甲酸醋或聚胺基 f酸醋-尿素製成’其是藉著異氰酸醋終端之胺基甲酸醋 預聚物及鏈延伸劑反應做為聚合物基材而獲得。使用在鍵 延伸劑中具某些比率之具有數量平均分子量細或更低的 ⑽及在分子中含三或多個活性含氫基團的組份為起始物 質’使得可能減少聚合物基材在高溫下的儲存彈性係數到 適當值。由於儲存彈性係數之適當的溫度依賴性改變,當 研磨層以外來物質劇烈磨擦時’聚合物基材容易且快速地 軟化’並且由於所產生的熱而變形’因此使得可能抑制外 來物質對要被研磨之表面的損傷。因此,本發明的研磨層 在抑制刮傷(產率改進)的效果上為優越的。因為不與外來 物質接觸的:部份研磨層具有相當低的溫度,聚合物基材 為堅硬的,並因此被要研磨之標的物的平坦性變高。 對研磨塾較佳的是:在研磨期間具有留持於漿之功能及 暫時留住研磨所產生粉末之功能的孔洞,必須在研磨時間 105684.doc 1379853 内形成。根據本發明之另一個較佳具體實施例的研磨墊具 有含聚合物基材的研磨層,該聚合物基材是由聚胺基甲酸 産曰或聚胺基甲酸酯-尿素製成,並且具有上述的彈性係數 改變的特性,並且水溶性顆粒分散在聚合物基材^。該水 溶性顆粒溶解於水中,或與在研磨期間,其與包含介質及 固體之淤漿接觸時,與要被排除的水膨脹’因此形成孔 洞。可獲得具尚硬度、大壓縮強度的研磨墊及要被研磨之 標的物的優良平坦性,因此具有尺寸優良均勻性、適於留 持淤漿的孔洞,在墊的表面層形成,由於上述結構而用來 留持研磨所需之淤漿,並且墊的内部具有無孔洞結構,其 中存在水溶性顆粒《因為具有優良斷裂強度及研磨抵抗力 之聚合物基材在本發明中獲得,在研磨期間,可抑制例如 從要被研磨標的物加於研磨墊之壓力的外力及以鑽石修整 器(dresser)修整對墊表面的變形及研磨,因此使得可能獲 得具有優良研磨穩定性及淤漿留持力和高移除速率的研磨 墊。1379853 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a polishing pad. More specifically, it relates to a polishing pad having an abrasive layer made of polyamino phthalate or polyurethane-urea having a special composition and capable of being subjected to high temperature and extreme grinding. The foreign matter as the abrasive layer is appropriately softened under the conditions to reduce the damage of the surface to be polished. This pad is advantageously used to polish the surface of a semiconductor wafer or the like. • [Prior Art] Chemical mechanical polishing (CMP) is a grinding technique that attracts a lot of attention and is capable of forming extremely flat surfaces. The CMP is carried out by allowing the slurry of the aqueous dispersion of the abrasive particles to flow downward from above through the surface of the polishing pad while the polishing pad and the surface to be polished are in sliding contact with each other. It is assumed that the variation in the spring constant of the polishing pad is suppressed by the temperature change to suppress the variation in the polishing performance caused by the increased temperature of the polishing surface and the frictional heat generated by the polishing surface (refer to U.S. Patent No. 6,293,852 and US Patent No. 6' 454,634). However, when the modulus of elasticity of the polishing pad is too high under extreme grinding conditions such as high grinding pressure or high resolution, the surface to be ground by I is easily subjected to, for example, the powder produced by grinding and contained in the polymerization. _ "It is difficult to reduce the damage of foreign substances to the surface by the foreign matter of the abrasive granules to the wound. The removal rate is a factor that greatly affects the productivity of CMp. That is, the removal rate can be increased by the amount of cracking remaining in the grinding crucible and greatly improved to 7 grinding to use the polyurethane foam containing CMp grinding crucible 105684.doc 1379853 containing the micro chamber (4) crucible. And keep the slurry in a hole (referred to as "hole") that is open to the surface of the resin foam. However, it is difficult to freely control the foaming of the polyurethane foam and it is also extremely difficult to control the uniform pore size and density over the entire area of the foam. As a result, this resulted in a difference in quality, removal rate, and processing state of the polishing pad made of the polyaminophthalate foam. A polishing pad obtained by dispersing a soluble product in a resin is known as a polishing pad which can easily control pores by foaming (JP_A 8-500622, JP_A 2000-33552, JP-A 2000-34416, and JP_A 2001- 334455) (The term "JP-A" as used herein means "unexamined published patent application". In addition, JP-A 8-500622 and JP-A 2000-33552 propose the effectiveness of a polishing pad containing a soluble product. However, no research is done when these grinding pads are actually used on the substrate. In JP-A 2000-34416 and JP-A 2001-334455, the study is on the constituent materials of the polishing pad, and a stable polishing and removal rate improvement is observed. However, a more stable grinding and slurry retention is observed. Further improvements in reUinability and removal rate are needed for true grinding work. It is also desirable to further improve the flatness of the abrasive target. SUMMARY OF THE INVENTION The present invention has been constructed in view of the above circumstances. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide an abrasive pad which, under extreme grinding conditions in which the surface to be polished is damaged by foreign matter, causes little damage, and the elastic modulus of the abrasive layer tends to appropriately follow the temperature. Ascending and descending, the abrasive crucible has excellent grinding stability, retention in pulp and high removal rate, and is superior to the flattening of the target to be grounded by 105684.doc 1379853. Other objects and advantages of the present invention will become apparent from the following description. According to the invention, first of all, the above objects and advantages of the invention are achieved by a polishing pad having an abrasive layer made of polyurethane or polyurethane-urea, wherein the polyaminocarboxylic acid The ester or polyamino phthalate-urea is a cured reaction product of a mixture of an isocyanate terminated urethane prepolymer A and a chain extender B, the chain extender B having two or more in the molecule The isocyanate group reacts with an active hydrogen-containing group' and satisfies the following conditions "a"&"b": a_ the chain extender consists of 50 to 100% by weight of a chain having a number average molecular weight of 3 Å or less. An extender and 50 to 0% by weight of a chain extender having a number average molecular weight of more than 300; or b. 20 to 100% by weight of the chain extender having three or more active hydrogen-containing groups in the molecule a chain extender and 80 to 0% by weight of a chain extender having two active hydrogen-containing groups in the molecule; and the ratio of the storage elastic modulus of the polishing pad at 30 ° C to the storage elastic modulus at 60 ° C 2 to 15, and the pad is stored at 30 °C The ratio of the storage elastic modulus at 90 ° C the coefficient of elasticity of 4 to 20. According to the present invention, the above objects and advantages of the present invention are achieved by a polishing pad having an abrasive layer in which the abrasive layer is dispersed in a polyurethane or polyurethane-urea. Water soluble particles in the polymeric substrate. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT The present invention will be described in detail hereinafter. 105684.doc 1379853 It is important that the polishing pad first has to grind the large amount of the object to be polished on the surface of the object and rarely grind it in the crucible. The recess on the surface, and the entire surface must be smoothed at the end of the grinding.囡 " Therefore, the polishing pad desirably has a relatively high hardness such that the surface of the abrasive crucible does not deform and enters the recess on the surface to be ground. At the same time, when the grinding crucible has a high hardness, it is not a change in the 'transformability' and the foreign matter such as the powder produced by the grinding and the abrasive particle agglomerates contained in the aged slurry, and the damage to the surface to be ground ( The scratching is increased, thus reducing the yield of the accepted product. It is difficult to achieve high flatness and at the same time suppress scratches in the art of grinding. The polishing layer of the polishing pad of the present invention is made of polyurethane urethane or polyamine-based acid vinegar-urea, which is made by reacting an amino hydroxyacetate prepolymer and chain extender at the terminal of isocyanic acid vinegar. Obtained for the polymer substrate. Using a component having a number average molecular weight fine or lower in the bond extender (10) and a component containing three or more active hydrogen-containing groups in the molecule as a starting material' makes it possible to reduce the polymer substrate Store the elastic modulus at an elevated temperature to an appropriate value. Due to the appropriate temperature-dependent change in the storage elastic modulus, the polymer substrate is easily and rapidly softened when the material outside the polishing layer is strongly rubbed and deformed due to the heat generated, thus making it possible to suppress the foreign matter to be Damage to the ground surface. Therefore, the abrasive layer of the present invention is superior in suppressing the effect of scratching (improvement in yield). Since it is not in contact with foreign matter: a part of the abrasive layer has a relatively low temperature, the polymer substrate is hard, and thus the flatness of the object to be ground becomes high. Preferably, the abrasive crucible is such that it has a function of retaining the slurry during polishing and temporarily retaining the function of the powder produced by the grinding, and must be formed in the grinding time 105684.doc 1379853. A polishing pad according to another preferred embodiment of the present invention has an abrasive layer comprising a polymer substrate made of polyamine formate or polyurethane-urea, and It has the above characteristics of changing the modulus of elasticity, and the water-soluble particles are dispersed on the polymer substrate. The water-soluble particles are dissolved in water or, when in contact with a slurry containing a medium and a solid during grinding, expand with water to be excluded' thus forming pores. It is possible to obtain an excellent flatness of a polishing pad having a hardness and a large compressive strength and a target to be polished, and therefore having a hole having a uniform size and being suitable for retaining a slurry, which is formed on the surface layer of the pad due to the above structure And used to retain the slurry required for grinding, and the inside of the mat has a non-porous structure in which water-soluble particles are present. "Because of the polymer substrate having excellent breaking strength and grinding resistance, it is obtained in the present invention during grinding. It is possible to suppress, for example, an external force from the pressure of the object to be polished to the pressure of the polishing pad and trimming and grinding the surface of the pad with a diamond dresser, thereby making it possible to obtain excellent polishing stability and slurry retention. And a high removal rate polishing pad.
異II酸酯终端之胺基甲酸酯預聚物A 用於本發明之異氰酸酯終端的胺基甲酸酯預聚物A,是 藉著將在分子中具有兩或多個〇H基團之化合物γ與在分子 中具有兩或多個異氰酸酯基團的聚異氰酸酯反應而獲得, 異氰酸酯基團/OH基團的當量比率較佳為2或更高,更佳為 2至5,最佳為2_1至4 ^當.該當量比率變成低於2時,所獲 得之異氰酸酯終端之胺基甲酸酯預聚物的分子量變高,結 果為異氰酸酯終端之胺基曱酸酯預聚物的黏度升高。因 105684.doc •10· 1379853 此,加熱溫度必須進一步增加。此使得難以控制用來鑄造 聚胺基甲_基材的條件,因而所獲得之研磨塾的表現變 得不穩定。當該當量比率變成高於5時,在溫度升高時所 得聚合物基材之彈性係數減少得過度,因而在研磨墊上之 研磨表現的變動變得太大,因此使得研磨有缺陷地不穩 定。 雖然所得之異氰酸酯終端的胺基甲酸酯預聚物Α必需由 異氰酸酯終端的胺基f酸酯預聚物所組成,其可包含未反 應之起使物質,如:在分子中具有兩或多個基團的化 合物Y、或在分子中具有兩或多個異氰酸酯基團的聚異氰 酸醋。 對合成異氱酸酯終端的胺基甲酸酯預聚物A,溫度可被 升咼到50至90。(:,或如:三級胺或有機錫之金屬為基礎的 觸媒可視情兄地被用做反應觸媒。在分子中具有兩或多個 OH基團之化合物γ的實例包括在一個分子兩端具有基 團的二醇化合物、在分子中具有三或多個〇Η基團的多官 旎基多醇類及在分子中具有兩或多個〇Η基團的多官能基 低分子量醇類。 在—個分子兩端具有0Η基團的二醇化合物包括聚醚二 醇類,如:脂族聚醚二醇類、非環狀聚醚二醇類及芳香族 聚醚二醇類、聚酯二醇類、聚碳酸酯二醇類、聚己内酯二 醇類、自二醇及異氰酸酯之間的反應合成的多醇類及其他 夕醇類。這些多醇類可單獨或兩或多個組合使用。 月曰族聚醚二醇類包括聚乙二醇、聚丙二醇、聚丁二醇、 105684.doc 聚己二醇、聚庚二醇、聚癸二醇及以兩或多個離子可聚合 環狀化合物之開環共聚所獲得的聚醚二醇類。 上述離子可聚合環狀化合物的實例包括環氧乙烷、環氧 丙烷、環氧-1-丁③、環氧異丁烷、3,3_雙氯甲基環氧丙 烷、四氫呋喃、2-甲基四氫呋喃、3-甲基四氫呋喃、二噁 烷、二噁烷、四噁烷、環己烯氧化物、笨乙烯氧化物、環 氧氣丙烷、f基丙烯酸縮水甘油酯、烯丙基縮水甘油基 醚、碳酸烯丙基縮水甘油酯、丁二烯單氧化物、戊二烯單 氧化物、乙烯基環氧丙烷、乙烯基四氫呋喃、乙烯基環己 烯氧化物及環狀醚類,如:苯基縮水甘油基醚、丁基縮水 甘油基趟及笨曱酸縮水甘油醋。 以兩或多個離子可聚合環狀化合物之開環共聚所獲得的 聚醚二醇類包括由四氫呋喃及環氧丙烷組合、四氩呋喃及 2-曱基四氫呋喃組合、四氫呋喃及3_甲基四氫呋喃組合、 四氫呋喃及環氧乙烷組合、環氧丙烷及環氧乙烷組合及環 氧-1-丁烷及環氧乙烷組合所獲得的共聚物二醇類;由四氫 夫喃、環氧-1-丁院及環乳乙烧組合所獲得的三聚物二醇 類。 也可使用以上述離子可聚合環狀化合物及如:乙烯亞胺 之環狀亞胺、如:β-丙内酯或縮水乳酸(lactide)甘醇酯的 環狀内酯酸、或二曱基環丙基石夕氧院之開環共聚所獲得的 聚醚二醇類。上述脂族聚醚二醇類的商業上可獲得產物包 括(三菱化學公司(Mitsubishi Chemical Corporation)的) PTMG650、PTMG1000 及 PTMG2000、(Asahi Denka Co” 105684.doc •12· 1379853The meta-acid ester terminal urethane prepolymer A is used in the isocyanate terminal urethane prepolymer A of the present invention by having two or more 〇H groups in the molecule. The compound γ is obtained by reacting a polyisocyanate having two or more isocyanate groups in the molecule, and the equivalent ratio of the isocyanate group/OH group is preferably 2 or more, more preferably 2 to 5, most preferably 2_1. When the equivalent ratio becomes less than 2, the molecular weight of the obtained isocyanate terminated urethane prepolymer becomes high, and as a result, the viscosity of the aminocyanate prepolymer of the isocyanate terminal increases. . Since 105684.doc •10· 1379853, the heating temperature must be further increased. This makes it difficult to control the conditions for casting the polyurethane substrate, and thus the performance of the obtained abrasive enamel becomes unstable. When the equivalent ratio becomes higher than 5, the elastic modulus of the polymer substrate obtained when the temperature is raised is excessively reduced, so that the variation in the polishing performance on the polishing pad becomes too large, so that the polishing is defective and unstable. Although the resulting isocyanate terminated urethane prepolymer must be composed of an isocyanate terminated aminof-ester prepolymer, it may comprise unreacted starting materials, such as two or more in the molecule. a group of compound Y, or a polyisocyanate having two or more isocyanate groups in the molecule. For the synthesis of the isocyanate terminal urethane prepolymer A, the temperature can be raised to 50 to 90. (:, or, for example, a catalyst based on a metal of a tertiary amine or an organotin is used as a reaction catalyst. An example of a compound γ having two or more OH groups in a molecule is included in one molecule. a diol compound having a group at both ends, a polyfunctional thiol polyol having three or more sulfonium groups in the molecule, and a polyfunctional low molecular weight alcohol having two or more sulfonium groups in the molecule The diol compound having a fluorene group at both ends of the molecule includes polyether diols such as aliphatic polyether diols, acyclic polyether diols, and aromatic polyether diols. Polyols, polycarbonate diols, polycaprolactone diols, polyols synthesized from the reaction between diols and isocyanates, and other alcohols. These polyols may be used alone or in combination. A plurality of combinations. The ruthenium polyether diols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, 105684.doc polyhexylene glycol, polyheptanediol, polydecanediol, and two or more a polyether diol obtained by ring-opening copolymerization of an ion-polymerizable cyclic compound. The above ion-polymerizable cyclic compound Examples include ethylene oxide, propylene oxide, epoxy-1-butene 3, isobutylene oxide, 3,3-dichloromethyl propylene oxide, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyl Tetrahydrofuran, dioxane, dioxane, tetraoxane, cyclohexene oxide, stupid ethylene oxide, epoxide propane, glycidyl f-methacrylate, allyl glycidyl ether, allyl glycidyl carbonate Ester, butadiene monooxide, pentadiene monooxide, vinyl propylene oxide, vinyl tetrahydrofuran, vinyl cyclohexene oxide and cyclic ethers, such as phenyl glycidyl ether, butyl Glycidyl hydrazine and alumic acid glycidol vinegar. Polyether diols obtained by ring-opening copolymerization of two or more ionic polymerizable cyclic compounds include tetrahydrofuran and propylene oxide combination, tetra arfurfuran and 2- Copolymer obtained by combination of mercaptotetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, tetrahydrofuran and ethylene oxide combination, propylene oxide and ethylene oxide combination and epoxy-1-butane and ethylene oxide combination Glycols; from tetrahydrofuran, epoxy-1-butyl a terpolymer diol obtained by a combination of the above-mentioned ionic polymerizable cyclic compound and a cyclic imine such as ethyleneimine, such as β-propiolactone or lactide (lactide). a polyether diol obtained by ring-opening copolymerization of a cyclic lactone acid of a glycol ester or a dimercaptocyclopropyl oxalate. Commercially available products of the above aliphatic polyether diols include ( Mitsubishi Chemical Corporation) PTMG650, PTMG1000 and PTMG2000, (Asahi Denka Co) 105684.doc •12· 1379853
Ltd.的)P4O0及P1000、(Asahi Glass Urethane Co” Ltd.的) Exenol 720、1020及 20202、PEG1000、(NOF Corporation 的)Unisafe DC1100及 DC1800、(Hodogaya Chemical Co., Ltd.的)PTG2000、PTG1000、PTG400 >5. PTGL2000 ' Z-3001-4、Z-3001-5、PBG2000A、PBG2000B、(Dai-Ichi Kogyo Seiyaku Co” Ltd.的)EO/B04000 及 EO/B02000及 (BASF Japan Co.,Ltd.的)Poly THF 250、Poly THF 650、 Poly THF 1000、Poly THF 1800及 Poly THF 2000。Ltd.) P4O0 and P1000, (Asahi Glass Urethane Co" Ltd.) Exenol 720, 1020 and 20202, PEG1000, (NOF Corporation) Unisafe DC1100 and DC1800, (Hodogaya Chemical Co., Ltd.) PTG2000, PTG1000 , PTG400 > 5. PTGL2000 'Z-3001-4, Z-3001-5, PBG2000A, PBG2000B, (Dai-Ichi Kogyo Seiyaku Co" Ltd.) EO/B04000 and EO/B02000 and (BASF Japan Co., Ltd.) Poly THF 250, Poly THF 650, Poly THF 1000, Poly THF 1800, and Poly THF 2000.
非環狀聚醚二醇類包括氫化雙酚A的環氧烷類加成二醇 類、氫化雙酚F的環氧烷類加成二醇類及M-環己烷二醇的 環氧烷類加成二醇類。再者,芳香族聚醚二醇類包括雙酚 A的環氧烷類加成二醇類、雙酚F的環氧烷類加成二醇類、 對苯二酚的環氧烷類加成二醇類、萘氫醌 (naphthohydroquinone)的環氧烧類加成二醇類及蒽氫酿 (anthrahydroquinone)的環氧炫類加成二醇類。上述芳香族 聚醚二醇類的商業上可獲得產物包括(NOF Corporation的) Uniol DA400、DA700、DA1000及 DA4000 ° 聚酯二醇類是以多氫醇與多驗性酸反應而獲得。該多氫 醇的實例包括乙二醇、聚乙二醇、丙二醇、聚丙二醇、四 亞曱基二醇、聚四亞甲基二醇、1,6-己烷二醇、新戊二 醇、1,4-環己烷二曱醇、3-曱基-1,5-戊烷二醇、1,9-壬烷二 醇及2-甲基-1,8-辛烷二醇。多鹼性酸的實例包括鄰苯二甲 酸、間苯二甲酸、對苯二曱酸、順丁烯二酸、反丁烯二 酸、己二酸及癸二酸。 105684.doc -13- 上述聚酯二醇類之商業上可獲得產物包括(Kuraray Co., Ltd.的)〖11哪〇1?-2010、?-1010、1^2010、1^1010、八-2010、A-1010、F-2020、F-1010、PMIPA-2000、PKA-A、 PNOA-2010及 PNOA-101。 聚碳酸酯二醇類包括的聚四氫呋喃之聚碳酸酯類及1,6-己烷二醇之聚碳酸酯類。聚碳酸酯二醇類的商業上可獲得 產物包括(Nippon Polyurethane Co_,Ltd.的)DN-980、 981、982及 983、(PPG Industries, Inc.的)PC-800、(BASF AG的)PC-THF-CD。 聚己内酯二醇類是以反應ε-己内酯與一個二醇反應而獲 得。該二醇的實例包括乙二醇、聚乙二醇、丙二醇、聚丙 二醇、四亞甲基二醇、聚四亞甲基二醇、1,2-聚丁二醇、 1,6-己烷二醇、新戊二醇、1,4-環己烷二甲醇及1,4-丁二 醇。這些聚己内酯二醇類是商業上可獲得的產物,如: (Daicel Chemical Industries,Ltd.的)Praccel 205、205 AL、 212、212AL、220及 220AL。 在分子中具有三或多個羥基團的多官能基多醇類包括聚 醚多醇類、聚酯多醇類、聚碳酸酯多醇類、聚醚碳酸酯多 醇類、聚酯碳酸酯多醇類及以下式代表的多官能基加成反 應產物:The acyclic polyether diols include alkylene oxide addition diols of hydrogenated bisphenol A, alkylene oxide addition diols of hydrogenated bisphenol F, and alkylene oxides of M-cyclohexane diol. Addition diols. Further, the aromatic polyether diols include alkylene oxide addition diols of bisphenol A, alkylene oxide addition diols of bisphenol F, and alkylene oxide addition of hydroquinone. Epoxy-based addition diols of diols, naphthohydroquinones, and epoxy-based addition diols of anthrahydroquinone. Commercially available products of the above aromatic polyether diols include Uniol DA400 (DAF Corporation), DA700, DA1000 and DA4000 ° polyester diols which are obtained by reacting a polyhydric alcohol with a polynuclear acid. Examples of the polyhydric alcohol include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetradecylene glycol, polytetramethylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 3-mercapto-1,5-pentanediol, 1,9-nonanediol, and 2-methyl-1,8-octanediol. Examples of the polybasic acid include phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, and sebacic acid. 105684.doc -13- The commercially available products of the above polyester diols include (11) 〇1?-2010, (Kuraray Co., Ltd.)? -1010, 1^2010, 1^1010, VIII-2010, A-1010, F-2020, F-1010, PMIPA-2000, PKA-A, PNOA-2010 and PNOA-101. The polycarbonate diols include polycarbonates of polytetrahydrofuran and polycarbonates of 1,6-hexanediol. Commercially available products of polycarbonate diols include (Nippon Polyurethane Co., Ltd.) DN-980, 981, 982, and 983, (PPG Industries, Inc.) PC-800, (BASF AG) PC -THF-CD. Polycaprolactone diols are obtained by reacting ε-caprolactone with a diol. Examples of the diol include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6-hexane Glycol, neopentyl glycol, 1,4-cyclohexane dimethanol and 1,4-butanediol. These polycaprolactone diols are commercially available products such as: (Daicel Chemical Industries, Ltd.) Praccel 205, 205 AL, 212, 212 AL, 220 and 220 AL. Polyfunctional polyols having three or more hydroxyl groups in the molecule include polyether polyols, polyester polyols, polycarbonate polyols, polyether carbonate polyols, polyester carbonates Alcohols and polyfunctional addition reaction products represented by the following formula:
CH20 (CH2CH(CH3)0) aHCH20 (CH2CH(CH3)0) aH
II
CHO (CH2CH(CH3)0) bHCHO (CH2CH(CH3)0) bH
I CH20 (CH2CH(CH3)0) ch 105684.doc •14· 1379853 其中a、b及c各獨立為〇至100的整數,限制條件為6及( 不是同時為〇, 並且以加成環氧丙烷到甘油而獲得,其所有是從如:甘 油、二甲基醇丙烧、1,2,6.己烧三醇或三乙醇胺的三醇、 或如:季戊四醇或四甲基醇環己院的四醇為起始多醇組份 製造。三官能基加成反應產物為商業上可獲得的產物, 如.(NOF Corporation的)Uniol TG330。 在一個分子中具有兩或多個羥基團的多官能基低分子量 醇類包括乙二醇、1,3-丙炫二醇、Μ· 丁貌二醇、μ己院 二醇、1,4-雙(羥基乙氧基)苯及三甲基醇丙烷。 在分子中具有兩或多個〇Η基團之上述化合物丫中,聚醚 多醇類是較佳的,因為聚合物經水解的分解被抑制,並且 聚醚二醇類為更佳的,因為其減少未反應〇11基團的數 目,改進抗水性。 在一個分子中具有兩或多個〇Η基團之化合物丫的數量平 均分子量是較佳為300至2,000的範圍,更佳為4〇〇至 1,500。兩或多個化合物可組合使用做為化合物γ。在此情 況下,化合物Υ之數量平均分子量是考慮這些化合物之使 用比率及數量平均分子量而獲得的算術平均值。當數量平 均分子量低於300時,所獲得之聚合物基質的硬度及彈性 係數變得太高’因而當使用所得之研磨墊時,大量的到傷 趨向於被產生。當數量平均分子量高於2,_時’所獲得 之聚合物基質的硬度及彈性係數變得太低,因而所得之= 磨墊時趨向於在平坦化上不良。 105684.doc 1379853 用於本發明之聚異氰酸酯時被用做在分子中具有至少兩 個異氛酸酯基團的化合物。該聚異氰酸酯化合物的實例包 括芳香族二-或三-異氰酸酯類、脂族二-或三-異氰酸酯 類、非環狀二-或三-異氰酸酯類及聚異氰酸酯類的改質產 物。芳香族二-或三-異氰酸酯類包括2,4_甲苯伸基二異氰 酸龜、2,6-曱笨伸基二異氰酸酯、苯伸基二異氰酸酯、二 甲苯伸基二異氰酸酯、四甲基二甲苯伸基二異氰酸醋、 2’2'-二笨基甲烷二異氰酸酯、2,4,_二笨基甲烷二異氰酸 酯、4’4’-二笨基甲烷二異氰酸酯、甲聯苯胺二異氰酸酯、 雙(4-異氰酸酯-3-甲基苯基)曱烷、三苯基甲烷三異氰酸酯 及1,5·萘二異氰酸酯。脂族二_或三_異氰酸酯類包括丨,心四 伸甲基二異氰酸酯、1,6-六伸甲基二異氰酸酯、三甲基 六伸甲基二異氰酸酯、1,10-十伸曱基二異氰酸酯、離胺酸 一異氰酸醋及1,3,6-六伸甲基三異氰酸醋。非環狀二-哎三· 異氰酸ί旨類包括異佛樂酮(isophorone)及經氫化的二苯某 甲烷二異氰酸酯。聚異氰酸酯類的改質產物包括多氫醇與 聚異氰酸酯的加成物、具有聚異氰酸酯環的二聚物、三聚 物、脲基甲酸鹽改質產物、尿素改質的聚異氰酸酯類及 burette改質的聚異氰酸酯類。這些之外,芳香族二·或= 異氰酸酯類及脂族二-或三-異氰酸酯類為較佳,並且芳香 族二異氰酸醋類及脂族二異氰酸酯類為特佳。上述的聚異 氰酸醋類可單獨、或兩或多個組合使用。 因此,所得之異氰酸酯終端之胺基甲酸酯預聚物可單 獨、或兩或多個組合使用。 105684.doc -16- 1379853I CH20 (CH2CH(CH3)0) ch 105684.doc •14· 1379853 where a, b and c are each independently an integer from 〇 to 100, with a constraint of 6 and (not simultaneously 〇, and addition of propylene oxide) Obtained by glycerol, all of which are from triols such as glycerol, dimethyl alcohol-propylate, 1,2,6-hexanol or triethanolamine, or such as: pentaerythritol or tetramethylol The tetraol is produced as the starting polyol component. The trifunctional addition reaction product is a commercially available product such as Uniol TG330 (of NOF Corporation). Polyfunctional having two or more hydroxyl groups in one molecule. Base low molecular weight alcohols include ethylene glycol, 1,3-propanediol, hydrazine butyl diol, hexamethylene glycol, 1,4-bis(hydroxyethoxy)benzene, and trimethylolpropane Among the above compounds having two or more anthracene groups in the molecule, polyether polyols are preferred because decomposition of the polymer by hydrolysis is inhibited, and polyether glycols are more preferred, Improved water resistance because it reduces the number of unreacted 〇11 groups. Compounds having two or more sulfonium groups in one molecule The number average molecular weight is preferably in the range of 300 to 2,000, more preferably 4 to 1,500. Two or more compounds may be used in combination as the compound γ. In this case, the number average molecular weight of the compound is The arithmetic mean obtained by considering the use ratio of these compounds and the number average molecular weight. When the number average molecular weight is less than 300, the hardness and the modulus of elasticity of the obtained polymer matrix become too high' thus when the obtained polishing pad is used A large amount of damage tends to be produced. When the number average molecular weight is higher than 2, _, the hardness and elastic modulus of the polymer matrix obtained become too low, so that the resulting pad = tends to be flattened. 105684.doc 1379853 When used in the polyisocyanate of the present invention, it is used as a compound having at least two isocyanate groups in the molecule. Examples of the polyisocyanate compound include aromatic di- or tri-isocyanates, Modified products of aliphatic di- or tri-isocyanates, acyclic di- or tri-isocyanates and polyisocyanates. Aromatic di- or tri-isocyanates Including 2,4-toluene diisocyanate, 2,6-indole diisocyanate, phenylexene diisocyanate, xylenesyl diisocyanate, tetramethyl xylene exo-diisocyanate , 2'2'-diphenylmethane diisocyanate, 2,4,_diphenylmethane diisocyanate, 4'4'-diphenylmethane diisocyanate, methylbenzidine diisocyanate, bis(4-isocyanate-3) -Methylphenyl)decane, triphenylmethane triisocyanate and 1,5-naphthalene diisocyanate. Aliphatic di- or tri-isocyanates include hydrazine, tetramethylammonium diisocyanate, 1,6-hexa-extension Methyl diisocyanate, trimethylhexamethylene diisocyanate, 1,10-decyldecyl diisocyanate, lysine monoisocyanate and 1,3,6-hexamethyl-triisocyanate . Acyclic bis-indolyl isocyanate includes isophorone and hydrogenated diphenyl methane diisocyanate. Modification products of polyisocyanates include adducts of polyhydric alcohols and polyisocyanates, dimers with polyisocyanate rings, trimers, allophanate modified products, urea-modified polyisocyanates and burettes. Modified polyisocyanates. In addition to these, aromatic di- or = isocyanates and aliphatic di- or tri-isocyanates are preferred, and aromatic diisocyanates and aliphatic diisocyanates are particularly preferred. The above polyisocyanates may be used singly or in combination of two or more. Therefore, the obtained isocyanate terminal urethane prepolymer may be used singly or in combination of two or more. 105684.doc -16- 1379853
鏈延伸劑B 在本發明中之鏈延伸劑是在分子中具有兩或多個能夠與 異氰酸酯終端之胺基甲酸酯預聚物A的異氰酸酯基團反應 之活性氫宫能基團的化合物。具有活性氫之官能基團的實 例包括0H基團、一級或二級胺基團及羧基團。 具有0H基團之化合物的實例包括是與在分子中具有兩 或多個0H基團之化合物γ那些相同的,該分子列舉上述之 異氰酸酯終端的胺基甲酸酯預聚物A。 具有一級胺基團或二級胺基團的化合物是例如多胺化合 物°多胺化合物的實例包括有機二胺化合物,如:3,3,_二 氯-4,4’·二胺基二笨基曱烷、氣笨胺改質之二氣基二胺基 二苯基甲烷、1,2-雙(2-胺基苯基硫基)乙烷、三伸甲基二 醇-二-對-胺基苯甲酸酯及3,5-雙(甲基硫基)_2,6_甲苯二 胺也可使用在分子中具有三或多個一級胺基團或二級胺 基團的化合物。 具有羧基團之化合物的實例包括脂族、芳香族、非環狀 及雜環二敌酸類、三叛酸類及四缓酸類。 月曰族二羧酸類包括草酸、丙二酸、丁二酸、戊二酸、己 -一酸及壬二酸。 芳香族二羧酸類包括鄰苯二甲酸、間苯二甲酸及對苯二 甲酸。芳香族四羧酸類包括均笨四甲酸。非環狀二羧酸類 包括環己基二羧酸》雜環二羧酸類包括萘二羧酸。非環狀 三羧酸類包括檸檬酸及烏頭酸。 這些化合物可單獨或兩或多個組合使用。這些之外,具 I05684.doc -17· 1379853 有〇H基團或胺基團的化合物為較佳,因為其與異氛酸醋 基團具有高反應性,並且具有〇H基團的化合物為特佳, 因為其具有用於製程中處理的適當反應性。Chain Extender B The chain extender in the present invention is a compound having two or more active hydrogen cation groups capable of reacting with an isocyanate group of a urethane prepolymer A of an isocyanate terminal in a molecule. Examples of the functional group having an active hydrogen include an OH group, a primary or secondary amine group, and a carboxyl group. Examples of the compound having a 0H group include the same as those of the compound γ having two or more OH groups in the molecule, which exemplifies the above-mentioned isocyanate terminal urethane prepolymer A. A compound having a primary amine group or a secondary amine group is, for example, a polyamine compound. Examples of the polyamine compound include an organic diamine compound such as: 3,3,-dichloro-4,4'.diamine-based Dihydrocarbyldiaminodiphenylmethane, 1,2-bis(2-aminophenylthio)ethane, tris-methylglycol-di-pair-modified by decane and gas Aminobenzoic acid esters and 3,5-bis(methylthio)_2,6-toluenediamine can also be used as compounds having three or more primary amine groups or secondary amine groups in the molecule. Examples of the compound having a carboxyl group include aliphatic, aromatic, acyclic, and heterocyclic diacyl acids, tritoponic acid, and tetra-hypo-acid. The ruthenium dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, hexamic acid and sebacic acid. The aromatic dicarboxylic acids include phthalic acid, isophthalic acid and terephthalic acid. Aromatic tetracarboxylic acids include the quaternary tetracarboxylic acid. Acyclic dicarboxylic acids include cyclohexyl dicarboxylic acid. Heterocyclic dicarboxylic acids include naphthalene dicarboxylic acid. Acyclic tricarboxylic acids include citric acid and aconitic acid. These compounds may be used singly or in combination of two or more. In addition to these, a compound having a hydrazine H group or an amine group is preferred because it has high reactivity with an oleic acid group and a compound having a hydrazine H group is a compound of the formula I05684.doc -17·1379853 Particularly preferred because it has the appropriate reactivity for processing in the process.
在本發明令之鏈延伸_是在分子卞具有兩或多個含活 性氫官能基團的化合物、或在分子中具有兩個含活性氫官 能基團之化合物與在分子中具有三或多個含活性氫官能基 團之化合物的混合物。為導致研磨墊之彈性係數隨溫度上 升的適當減少是本發明的一個特色,在分子中具有三戋多 個含活性氫官能基團的化合物必須被包含的份量是2 〇至 100重量%、較佳為30至_重量%,以鏈延伸劑總量為1〇〇 重量%基礎。當在分子中具有三或多個含活性氫官能基團 之化合物份量小於20重量%時,研磨墊之彈性係數隨溫度 上升的減少變小,並且在要被研磨之標的物上容易發生刮 傷。當在分子中具有三或多個含活性氫官能基團之化合物 份量小於20重量%時,藉著在聚合物基質以鑽石修整器修 整而斷裂之後所維持之聚合物延伸所形成的突出物變大, 因而在研磨墊之表面上的大聚合物突出物在數量上增加, 並且在研磨期間進入在標的物上凹處’結果是減少平坦 化。 除了上述條件之外,在本發明中之鏈延伸劑B包含50至 100重量%之具有數量平均分子量300或更低的鏈延伸劑, 較佳為50至1〇〇重量%之具有數量平均分子量25〇或更低的 鏈延伸劑’以鏈延伸劑總量為100重量%基礎。具有數量 平均分子量高於3〇〇的鏈延伸劑可被包含份量〇至50重量 105684.doc -18- 1379853 0/〇。當具有敫I平均分子量300或更低之鏈延伸劑的份量 是小於50重量%,在獲得之聚合物基質中硬鏈段及軟鏈段 之間的相分離變得不完全,並且彈性係數隨溫度上升之減 少變得過度,結果是研磨墊之研磨表現上的變動變大,因 此使得研磨不穩定。由於此不完全的相分離,發生聚合物 基質的水吸故,因此導致在研磨墊的硬度上缺陷地減少。 用來製造本發明之異氰酸酯終端之胺基曱酸酯預聚物A 的鏈延伸劑B及在分子中具有兩或多個〇H基團的化合物 Y,較佳使用的比率是化合物γ之數量平均分子量對鏈延 伸劑B之數量平均分子量較佳為3或更多,更佳為4至1〇。 當此數量平均分子量比率低於3時,在獲得之聚合物基質 中硬鍵段及軟鏈段之間的相分離趨向於變得不完全,並且 彈性係數隨溫度上升之減少趨向於變得過度,結果是研磨 墊之研磨表現上的變動趨向於變大,因此使得研磨不穩 定。 當許多化合物被用於與化合物Y及鏈延伸劑B組合時, 化合物Y之數量平均分子量及鏈延伸劑B之數量平均分子 量考慮許多化合物之比率及數量平均分子量而被計算的算 術平均值® 起始物質(異氟酸酯终端之胺基甲酸酯預聚物A及鏈延伸劑 B)之混合物及固化反應 在會變成形成本發明研磨墊之研磨層聚合物基質的聚胺 基甲酸自曰或聚胺基甲酸酯·尿素合成反應中,異氰酸酯終 端之胺基甲酸酯預聚物A及具有含活性氫官能基團之鏈延 105684.doc •19· 1379853 伸劑B的份量,是使得在鏈延伸劑b中包含之含活性氫官 能基團對在異氰酸酯終端之胺基甲酸酯預聚物A中所含之 異氰酸酯基團的莫耳比率,較佳為1/0.9至1/14,更佳為 1/0.95至1/1 _3 »當含活性氫基團對異氰酸酯基團的莫耳比 率落到低於0_9時,大量的未反應含活性氫基團留著,並 且所獲得之聚胺基甲酸酯變得在抗水性、抗鹼性及抗酸性 上為不良的。當異氰酸酯基團的莫耳比率超過14時,大 量的未反應含活性氫基團留在聚合反應的末期,並且隨時 間經過、藉著濕氣導致交聯反應,並且所得之聚合物基質 變得脆弱。 較佳地’在起始物質(異氰酸酯終端之胺基甲酸酯預聚 物A及鏈延伸劑B)混合之前’真空除泡被進行,同時起始 物質在高於其變成液體之溫度的溫度下被加熱,並且然後 其混合在一起。研磨表現可以避免由於製程、被包含在所 得研磨層中的發泡而被穩定。 在起始物質(異氰酸酯終端之胺基甲酸酯預聚物A及鏈延 伸劑B)被稱重並置於攪拌容器中之後,起始物質可藉著使 用具有1至3個元件、具泡沫不包含之攪拌力的反轉攪拌器 混合在一起。當考慮連續生產時,較佳使用配備獨立授拌/ 除泡槽之用於異氰酸酯終端之胺基曱酸酯預聚物A及鏈延 伸劑B的鑄造機及能夠連續混合兩種不同起始物質的線形 混合器。 在聚合物基質之合成反應中,起始物質的上述混合物被 加熱,提供熱能,或視情況地使用反應促進劑,用來促進 105684.doc -20- 1379853 反應。反應促進劑的實例包括四級胺類,如:三乙基胺、 苄基二甲基胺、三乙烯二胺、四甲基丁烷二胺及2甲基-三 乙烯二胺;錫化合物,如:醋酸二丁基錫、二月桂酸二丁 基錫、順丁烯二酸二丁基錫、二·2_乙基_己酸二丁基錫、 二醋酸二月桂基錫及二醋酸二辛基錫;及二偶氮-雙環烯 及其有機酸鹽類。 當研磨墊被用於半導體晶圓時,為抑制殘餘金屬含於研 磨層中,不使用反應促進劑;或當使用反應促進劑時,較 佳地使用四級胺類、二偶氮_雙環烯或其鹽。 聚合物基質之合成反應的溫度、時間及壓力不特別限 制。合成反應的第一階段較佳地是在反應到某些程度之 後,聚合物基質可從金屬鑄模移除的條件下進行,使得抑 制其厚度及可改變性《例如:反應較佳地在3〇至17(rc下 進行3分鐘至24小時。反應更佳地在5〇至13〇。〇下進行5分 鐘至3小時。雖然反應可在此第一階段中完成,聚合物基 質在80至150°C下維持3至μ小時,以進行第二階段的反 應,使得進一步完成反應。 由上述反應獲得之研磨墊的研磨層Sh〇re d硬度較佳為 3〇或更多,更佳為40至90,最佳為5〇至80。當Sh〇re D硬 度為30或更多時,加到要被研磨之標的物的壓力可為大, 並且因此移除速率可改進。The chain extension in the present invention is a compound having two or more active hydrogen-containing functional groups in the molecular oxime, or a compound having two active hydrogen-containing functional groups in the molecule and having three or more in the molecule A mixture of compounds containing active hydrogen functional groups. A suitable reduction in the coefficient of elasticity of the polishing pad as a function of temperature is a feature of the present invention. The compound having three or more active hydrogen-containing functional groups in the molecule must be included in an amount of from 2 Å to 100% by weight. It is preferably 30 to _% by weight based on the total amount of the chain extender of 1% by weight. When the amount of the compound having three or more active hydrogen-containing functional groups in the molecule is less than 20% by weight, the elastic modulus of the polishing pad decreases with an increase in temperature, and scratching is liable to occur on the target to be polished. . When the amount of the compound having three or more active hydrogen-containing functional groups in the molecule is less than 20% by weight, the protrusion formed by the polymer extension maintained after the polymer matrix is trimmed by the diamond dresser is changed. Large, thus the large polymer protrusions on the surface of the polishing pad increase in number and enter the recess in the target during grinding' as a result of reduced planarization. In addition to the above conditions, the chain extender B in the present invention contains 50 to 100% by weight of a chain extender having a number average molecular weight of 300 or less, preferably 50 to 1% by weight of a number average molecular weight. The chain extender of 25 Å or less is based on 100% by weight of the total chain extender. Chain extenders having a number average molecular weight above 3 Å can be included in the amount of 〇 to 50 weights 105684.doc -18-1379853 0/〇. When the amount of the chain extender having a 敫I average molecular weight of 300 or less is less than 50% by weight, the phase separation between the hard segment and the soft segment in the obtained polymer matrix becomes incomplete, and the modulus of elasticity varies. The decrease in the temperature rise becomes excessive, and as a result, the variation in the polishing performance of the polishing pad becomes large, so that the polishing is unstable. Due to this incomplete phase separation, water wicking of the polymer matrix occurs, thus causing a defect in the hardness of the polishing pad. The chain extender B used to produce the amino acid phthalate prepolymer A of the isocyanate terminal of the present invention and the compound Y having two or more hydrazine H groups in the molecule are preferably used in a ratio of the amount of the compound γ. The average molecular weight to chain extender B preferably has a number average molecular weight of 3 or more, more preferably 4 to 1 Torr. When the number average molecular weight ratio is less than 3, the phase separation between the hard bond segment and the soft segment in the obtained polymer matrix tends to become incomplete, and the decrease in the elastic modulus with temperature rise tends to become excessive. As a result, the variation in the polishing performance of the polishing pad tends to become large, thus making the polishing unstable. When many compounds are used in combination with Compound Y and Chain Extender B, the number average molecular weight of Compound Y and the number average molecular weight of Chain Extender B are calculated from the arithmetic mean of the ratio of many compounds and the number average molecular weight. Mixture of the starting material (isofluoride terminated urethane prepolymer A and chain extender B) and the curing reaction in a polyaminocarboxylic acid which will become the polymer matrix of the abrasive layer forming the polishing pad of the present invention Or the polyurethane-urea synthesis reaction, the isocyanate terminal urethane prepolymer A and the chain extension having the active hydrogen-functional group 105684.doc •19·1379853 stretcher B is The molar ratio of the active hydrogen-containing functional group contained in the chain extender b to the isocyanate group contained in the urethane prepolymer A of the isocyanate terminal is preferably from 1/0.9 to 1/1. 14. More preferably 1/0.95 to 1/1 _3 » When the molar ratio of the active hydrogen group to the isocyanate group falls below 0-9, a large amount of unreacted active hydrogen-containing groups remain and are obtained Polyurethane becomes resistant Resistance, alkali resistance and the acid resistance of the poor. When the molar ratio of the isocyanate group exceeds 14, a large amount of unreacted active hydrogen-containing groups remain at the end of the polymerization reaction, and the crosslinking reaction proceeds by moisture over time, and the resulting polymer matrix becomes fragile. Preferably, 'vacuum defoaming is carried out before the starting material (isocyanate terminated urethane prepolymer A and chain extender B) is mixed, while the starting material is at a temperature above the temperature at which it becomes liquid. It is heated down and then mixed together. The abrasive performance can be prevented from being stabilized by the process and by the foam contained in the resulting abrasive layer. After the starting materials (isocyanate terminated urethane prepolymer A and chain extender B) are weighed and placed in a stirred vessel, the starting material can have 1 to 3 components by use, without foaming The inverted agitator containing the stirring force is mixed together. When considering continuous production, it is preferred to use a casting machine for the isocyanate terminal amino phthalate prepolymer A and chain extender B equipped with an independent mixing/debubbing tank and to continuously mix two different starting materials. Linear mixer. In the synthesis of the polymer matrix, the above mixture of starting materials is heated to provide thermal energy or, optionally, a reaction promoter to promote the reaction of 105684.doc -20-1379853. Examples of the reaction accelerator include quaternary amines such as triethylamine, benzyldimethylamine, triethylenediamine, tetramethylbutanediamine, and 2-methyl-triethylenediamine; tin compounds, Such as: dibutyltin acetate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin di-ethyl-hexanoate, dilauryl tin diacetate and dioctyltin diacetate; and diazo - Bicycloolefins and their organic acid salts. When the polishing pad is used for a semiconductor wafer, a reaction accelerator is not used to suppress residual metal from being contained in the polishing layer; or when a reaction accelerator is used, a quaternary amine, diazo-biscycloolefin is preferably used. Or its salt. The temperature, time and pressure of the synthesis reaction of the polymer matrix are not particularly limited. The first stage of the synthesis reaction is preferably carried out under conditions in which the polymer matrix can be removed from the metal mold after the reaction to some extent, so that the thickness and the changeability are suppressed. For example, the reaction is preferably at 3 Torr. 3 to 24 hours at rc. The reaction is more preferably 5 to 13 Torr. The sputum is carried out for 5 minutes to 3 hours. Although the reaction can be completed in this first stage, the polymer matrix is between 80 and 150. The reaction of the second stage is carried out at ° C for 3 to μ hours to further complete the reaction. The polishing layer of the polishing pad obtained by the above reaction preferably has a hardness of 3 Å or more, more preferably 40. To 90, it is preferably from 5 to 80. When the Sh〇re D hardness is 30 or more, the pressure applied to the target to be ground may be large, and thus the removal rate may be improved.
水溶性顆粒C 本發明之另一個較佳具體實施例是具有包含水溶性顆粒 刀散於上述聚合物基質中之研磨層的研磨墊。在此研磨墊 105684.doc •21 - 1379853 中,在修整期間,該水溶性顆粒在其與水接觸時從聚合物 基質排除,或使用研磨墊時,在研磨期間、在墊之表面層 上從為水性分散物的淤漿排除。當該水溶性顆粒與水或 包含在要被溶解於水中之淤漿中的水接觸時、或當水溶性 顆粒與要被成膠之水膨脹時,此排除發生。再者,此溶解 或膨脹不只發生在其與水接觸時,也在其與含如:甲醇之 醇為基礎的溶劑的水性混合介質接觸時。 水溶性顆粒具有增加研磨墊之凹陷硬度、並且減少研磨 塾對要被研磨之標的物凹陷的效果,是除了形成孔動的效 果之外,藉著加壓在研磨墊《例如:藉著包含水溶性顆 粒’本發明之研磨塾的研磨層Shore D硬度可被設定到較 佳35或更多’更佳40至95,最佳為50至90 〇當Shore D硬 度為35或更多時’加到要被研磨之標的物的壓力可為大 的’並且因此移除速率可被改進。 另外’對被研磨之標的物之高研磨平坦性可以水溶性顆 粒的存在而達到。因此,該水落性顆粒較佳為固體,使得 其可對研磨墊確保足夠高的凹陷硬度。 構成水溶性顆粒的物質不被特別限制。例如:其為有機 水溶性顆粒或無機水溶性顆粒。有機水溶性顆粒之物質的 實例包括醣(多醣,如:澱粉、糊精、環狀糊精、乳糖、 甘露醇等)、纖維素(如:羥丙基纖維素、曱基纖維素等)、 蛋白質、聚乙烯基醇、聚乙烯基四氫芩咯酮、聚丙烯酸及 其鹽類、聚環氧乙烷、水溶性光敏樹脂、磺化聚異戊二烯 及續化異戊二婦共聚物❶無機水溶性顆粒之物質的實例包 105684.doc •22- 1379853 括醋酸鉀、硝酸鉀、碳酸鉀、碳酸氫鉀、氯化鉀、溴化 鉀、磷酸鉀及硝酸鎂。這些水溶性顆粒可單獨或兩或多個 組合使用。 水/容性顆粒具有平均顆粒直徑較佳為〇 i至5〇〇微米更 佳為0.5至300微米,再更佳為iiioo微米,特佳為1〇至9〇 微米。由排除水溶性顆粒形成的孔洞是大到較佳為〇」至 5〇〇微米,更佳為0.5至300微米,再更佳為1至1〇〇微米, 特佳為10至90微米。當水溶性顆粒之平均顆粒直徑為小於 〇.1微米時,所形成之孔洞在尺寸上變得比使用之研磨顆 粒更小,因而其難以獲得能夠完成留持於漿的研磨墊。當 平均顆粒直徑為大於500微米時,所形成之孔洞變得太 大,因而所獲得之研磨墊的機械強度及移除速率會降低。 水溶性顆粒的份量是較佳為〇·5至7〇體積%,更佳為【至 60體積%,特佳為2至45體積%,以聚合物基質及水溶性顆 粒構成之研磨層為100體積%基礎。當水溶性顆粒的份量 小於0.5體積❶/。時,孔洞不完全在所得之研磨墊中形成,並 且移除速率會降低。當水溶性顆粒的份量大於7〇體積% 時,其會難以完全避免存在於所得研磨墊之内部的水溶性 顆粒在研磨期間免於膨脹或溶解,因此使得難以維持研磨 墊之硬度及機械強度在適當值。 水溶性顆粒以重量計之份量計算可如下進行。例如:當 具有比重約1.5的醣被使用為水溶性顆粒、並且在反應結 束之後具有比重約1.15的聚胺基甲酸酯被用為聚合物基質 時’水溶性顆粒之份量較佳為〇 7至75.3重量%,更佳為^ 3 105684.doc -23- 1379853 至66.2重量% ’特別佳為2.6至51.6重量%,以研磨層為ίο。 重虽%基礎。當具有比重約1.15之聚丙稀酸、聚乙稀基四 氫苓咯酮或聚環氧乙烷被用做水溶性顆粒、並且在反應結 束之後具有比重約1.15的聚胺基甲酸酯被用為聚合物基質 時,水溶性顆粒之份量較佳為0.5至70重量。/。,更佳為i至 60重量%,特佳為2至45重量%,以研磨層為1〇〇重量%基 礎。再者,當具有比重約2之硝酸鉀的無機水溶性顆粒被 • 用做水溶性顆粒、並且在反應結束之後具有比重約115的 聚胺基甲酸輯被用為聚合物基質時,水溶性顆粒之份量較 佳為0.9至80.2重量%,更佳為1<7至72 3重量%,特佳為3 4 至58.7重量% ’以研磨層為100重量%基礎。 較佳的是當其曝露於研磨墊之表面層時,水溶性顆粒必 須只溶解在水中,並且當其存在於研磨墊内部時,必須不 吸收濕氣或膨脹,因此,水溶性顆粒較佳地在至少一部份 的表面具有用來抑制濕氣吸收的外殼。此外殼可物理性吸 • 附到水溶性顆粒、化學鍵結到水溶性顆粒、或藉著物理吸 附及化學鍵結與水溶性顆粒接觸。該外殼是以環氧樹脂、 聚亞醯胺樹脂、聚醯胺樹脂、矽酮樹脂或偶合劑製成,其 t纟此後敘述做為分散齊卜甚i當其只形成在一部份的水 溶性顆粒表面時,上述效果可被完全獲得。 當使用水溶性顆粒時,在所有起始物質混合之前,水溶 性顆粒較佳地先被分散在上述做為起始物質之異氰酸醋終 端的胺基甲酸8旨預聚物A及/或鏈延伸劑Bf 〇為避免水溶 性顆粒與起始物質溶液膨脹、並且在分散時溶解於起始物 105684.doc •24· 1379853 質溶液中,特佳的是該水溶性顆粒被分散在比鏈延伸劑B 具有更高分子量之異氰酸酯終端的胺基甲酸酯預聚物A 中。雖然分散方法不特別限制,較佳的是該水溶性顆粒被 添加,並且一點一點地分散’而異氰酸酯終端的胺基甲酸 醋預聚物A或鏈延伸劑B(或在分別容器中的兩者)在容器中 被攪拌’以獲得良好的分散液◦特佳的是該水溶性顆粒是 藉著使用能夠獲得剪切力的雙螺旋混合器而被分散。為避 免泡沫被包含在所得之研磨層中,除泡較佳地在水溶性顆 ® 粒分散期間或之後在減壓下進行。 分散輔助物可視情況地被使用。分散輔助物的實例包括 以酸酐基團、羧基團、羥基團、環氧基團、噁唑啩基團或 胺基團、非離子界面活性劑及偶合劑改質之均聚物、嵌段 共聚物及無規共聚物。 含水溶性顆粒分散其中之起始物質的混合及反應 以本發明含水溶性顆粒分散其中之聚胺基甲酸酯或聚胺 φ 基甲酸酯-尿素製成的研磨墊,是藉著進行混合含水溶性 顆粒分散其中之起始物質而獲得,並且聚合物基質的合成 反應以相同於起始物質(異氰酸酯終端的胺基甲酸酯預聚 • 物A及鏈延伸劑B)之混合及固化一項所述之方式,但除了 係、使用以上述方法製備之含水溶性顆粒分散其中的起始物 質(預聚物A、鏈延伸劑b或二者 其他可用的添加物 除了上述组份的組份可被添加到聚合物基質及/或水溶 性顆粒中,限制為不損害本發明的效果。 105684.doc -25- 1379853 為包括這些添加物於本發明之研磨墊的研磨層中,其必 須在聚合物基質形成之前被添加到起始物質中。 研磨墊 本發明之研磨墊的研磨層是藉著將起始物質混合物(異 氰酸醋终端的胺基甲酸酯預聚物a及鏈延伸劑B)、或以例 如在金屬鑄模中之上述方法製備的含水溶性顆粒分散其令 的起始物質混合物溶液反應而獲得。本發明之研磨墊的研 磨層的特徵在於:當其溫度藉著極度研磨條件所產生的磨 擦熱、或來自粗糙外來物質之過量壓力所產生的磨擦熱而 升高時,其彈性係數降到一個適當值。到傷可以減緩對要 被研磨之標的物的過量壓力、藉此減少彈性係數(軟化)而 避免。藉著抑制在溫度改變時彈性係數中的過量減少,在 研磨時的平坦化表現可被改進。為達到彈性係數隨溫度的 此適當改變,研磨層在30。(:之儲存彈性係數]^對在⑽它之 E·的比率是在2至15的範圍,較佳是3至1〇,並且在3〇<t之 E’對在90°C之E,的比率是在4至20的範圍,較佳是5至15。 儲存彈性係數E’必須被了解為:當具有寬度3毫米、厚 度3毫米及長度32毫米的條狀物被從片狀物上切出、並且 在測試溫度-20至13(TC、起初負載50克、動力偏差〇〇5% 及頻率10雷得(rad)/秒的張力模式下測量、並且在溫度升 高速率為5。(: /分鐘、使用商業可得動力黏彈性測試儀器 時,其為30°C或60°C下的值。 此研磨層可組成至少一部份的研磨墊的研磨表面。其組 成較佳是至少50%或更多的研磨表面,更佳是至少8〇0/〇或 105684.doc -26- 1379853 更多’特佳是至少90%或更多。整個研磨表面可由研磨層 構成。 除了研磨層之外的部份是例如用來藉著光學終點债測器 摘測終點的視窗部份。該視窗部份是以在波長1〇〇至3,_ 毫微米具有光學傳遞性0.1%或更多、較佳是2%或更多的 材質攀成,或在波長100至3,〇〇〇毫微米具有整體光學傳遞 性0.1%或更多、較佳是2%或更多的材質製成,而厚度為2 毫米。 再者,研磨墊的研磨層可為單層或包含另一層的複合 板。在複合板的情形下,研磨層為在複合板中形成研磨表 面的一層,除了研磨層之外的層是例如:安排在相反於研 磨層之研磨表面的表面上的支撐層及用來聯結支撐層及研 磨層在一起的鍵結層。 上述的支撐層為用來支撐在背面之研磨層的一層。雖然 支撐層的特徵性質不特別受限,支撐層較佳地比研磨層 軟。當該墊為軟支撐層時’若研磨層是例如〇 5毫米或更 少的薄,可能避免在研磨期間研磨層上升、或研磨層表面 弯曲,因此可能有穩定的研磨。支撐層的硬度較佳為90〇/〇 或更低的研磨層硬度’更佳為80%或更低,特佳為70%或 更低’並且通常是10。/。或更低。支撐層的Shore D硬度較佳 為7〇或更低,更佳為60或更低,特佳為50或更低,並且通 常是1或更低。 支樓層可為發泡的或不發泡的。支撐層的平面形狀不被 特別受限’並且可與研磨層相同或不同。支撐層的平面形 105684.doc -27· 1379853 .狀可為環形或多角形,例如:四角形。其厚度不被特別受 限,但較佳為0.1至5毫米,更佳為0.5至2毫米。當研磨層 .*有藉著光學終點偵測器偵測终點的視窗部份時,該視窗 料具有類似的形狀或相同的形狀,而不阻斷光通過視窗 部份或切斷傳遞光線的研磨層可無視窗部份被形成。 構成支撐層的材質不被㈣受限。較佳使用有機物質, 因為其容易鑄造成具有預先決定的形狀及性質並且可提 供適當的彈性。各種聚合物可被用做該有機物質。組成支 撐層的該有機物質可為經交聯的聚合❻、尚纟交聯的聚合 物、或不交聯的聚合物。 支撐層可由單層或多層組成。再者,支撐層及研磨層可 以熱融合直接組合在一起、或藉由上述的鍵結層。該鍵結 層是一個黏著劑的經固化層、或由壓敏性黏著劑製成的 層’如:黏著膠帶。 本發明之研磨墊的形狀不被特別受限,並且可為碟形、 φ 帶狀或滾筒狀。較佳地,其可適當地根據研磨機器選擇。 在使用前的研磨墊尺寸不被特別受限。在碟形研磨墊的情 況下,其直徑較佳為0.5至500公分,更佳為1〇至25〇公 • 分,特佳為20至2〇〇公分,並且其厚度是較佳大於〇1毫米 及100毫米或更少,特加為1至10毫米。 在其中使用此研磨墊的研磨製程不被特別受限。例如: 研磨墊可適當地在半導體晶圓的研磨中用於STI製程(淺溝 單離製程)中、用來形成由八丨或以金屬線的叙入 (damascene)製程、用來形成由A卜Cu或W製成之介層窗插 105684.doc -28- 1379853 塞(via plug)的嵌入製程、用來同時形成金屬線及介層窗插 塞的雙重鼓入製程、研磨界面緩衝層(interlayer)絕緣薄膜 (如:氧化膜、低k或BPSG)的製程、研磨氮化物薄膜(如: TaN或TiN)的製程及研磨聚矽或單晶矽的製程。 開放溝槽及/或凹處可在研磨墊的研磨表面上形成。溝 槽及/或凹處當做用來留住研磨時供應的淤漿,並且更均 勻地分佈彼到研磨表面》其也當做暫時留持由研磨所產生 之如粉末的廢物及用過的淤漿,並且變成用來洩出廢物到 外面的洩料路徑。溝槽的形狀不特別受限。其可為輪狀、 格狀、幅射狀及/或螺旋形。 輪狀溝槽的平面形狀不特別受限,並且可為圓形、如: 三角形、四角形或六角形的多角形、或橢圓形。在研磨墊 上形成之溝槽的數目較佳為二或多個。雖然溝槽的排置不 特別受限,溝槽可同心圓狀或非同心圓狀排置,或許多輪 狀溝槽可以在研磨表面之内部部份的單__輪狀溝槽環繞。 這些之外,較佳地溝槽被同心圓狀地排置。更佳地,許多 環形溝槽被同心圓狀地排置。具有環形溝槽被同心圓狀地 排置之研詩,優於上述功能的其他研磨^當環形溝槽 被同心圓狀地排置時’其在這些功能上為優良的並也容易 單-連續溝槽、或兩或多個不連續溝槽可形成格狀。 成格狀之型式的平面形狀不特別受限,並且可為多角形 :多㈣型式可為四角形’如··正方形、長方形、梯形 鑽石型、二角形、五角形或六角形。 105684.doc -29- 1379853 幅射狀溝槽是由許多從研磨塾之中心部份延伸到周圍的 溝槽所組成。該溝槽從中心部份延伸 形狀為直線、棋形或其組合。雖然溝槽可或不達到=的的 末端,至少其-較佳地達到周圍的末端,也就是該塾的側 面。例如:許多溝槽可由許多從中心部份延伸到周圍的直 線形溝槽組成,至少其一可達到該塾的側面,或許多溝槽 可由許多從令心部份延伸到周圍的直線形溝槽及許多從中 心部份及周圍部份之間一半位置延伸到周圍的直線形溝槽 所組成,至少其-可達到該墊的側面。許多溝槽可組成成 對的平行直線形溝槽。 -種螺旋形連續溝槽可形成,或可形成兩個在方向上互 相不同的螺旋形溝槽。再者,可形成兩個在方向上相同的 螺旋形溝槽’或可形成三或多個在方向上相同或不同的螺 旋形溝槽。 上述溝槽的尺寸不特別受限。例如:溝槽的寬度較佳為 〇.1毫米或更多,更佳為,更加為佳的是〇2至3 毫米’特佳為0·5至1毫米…般,難以形成具有寬度或最 小尺寸小於0·1毫米的溝槽。溝槽的深度較佳是〇1毫米或 更多,更佳為0.3至2.5毫米,更加為佳的是毫卡, 特佳為1.3至2毫米。當溝槽的深度是小於〇1毫米時,研磨 塾之使用壽命趨向於缺陷地變得太短。再者,溝槽之間的 間隔(在螺旋形溝槽之幅射方向上鄰近部份之間的最小距 離)較佳為0.05毫米或更多,更佳為〇〇5至1〇〇毫米,更加 為佳的是(Μ至1〇毫米,特佳為〇.5至2毫米。難以形成具有 105684.doc -30· 1379853 最小距離小於〇.05毫米的溝槽。為溝槽之寬度及鄰近溝槽 間距離之總和的斜度(pitch)較佳為〇15毫米或更多,更佳 為〇‘15至1()5毫米,更加為佳的是〇至13毫米,特佳為 至2.2毫米。 述較佳範圍可被組合。例如:溝槽較佳地具有寬度 0」毫米或更多、深度為.〇」毫米或更多並且最小距離為 〇.〇5毫米或更多’更佳地寬度n5毫米、深度為〇.3至η 毫米並且最小距離為0·05至1〇〇毫来,更加為佳的是寬度 0.2至3毫米、深度為m.2毫米並且最小距離為〇1至1〇: 米,特佳為宽度0.5Μ毫#、深度w 3至2毫米並且最小 距離為0.5至2毫米。 再者,溝槽内壁的表面粗糙度較佳為2〇微米或更小,更 佳為15微米或更小’最佳為1〇微米或更小,並且一般為 〇·〇5微米或更多。當表面粗糙度較佳為2〇微米或更小時, 研磨時的刮傷可被有效地避免。此表面粗糙度必須被了解 為在本發明之研磨墊使用之前的值。 “表面粗链度較佳為2 0微米或更小時,大變化不存在。 當大變化不存在時,例如:形成溝槽時產生之碎屑的特大 突出物,在研磨期間與刮傷的結果被排除。再者,刮傷會 在研磨期間由於壓力或磨擦熱、藉著壓縮所形成的外來物 質、或藉著研磨所產生之經排除突出物及粉末、或包含於 淤漿之固體間的互相作用而發生。突出物可在修整期間被 排除,導致相同的不便。 再者,當表面粗糙度較佳為20微米或更小時,刮傷可被 105684.doc 1379853 避免,並且溝槽的功能、特別是分佈淤漿到研磨表面的功 能’及洩出廢物到外面的功能,可有效地獲得。 上述凹處的平面形狀不特別受限,例如:其可為環形或 夕角形’如.三角%、四角形或五角形、或橢圓形。凹處 的可選擇形式也不特別受限。例如:其可為由平坦側面及 底面所形成的形狀(在開放面及底面之transverse方向上的 尺寸可為相同,在開放面的尺寸可比在底面的尺寸更大, 或在底面的尺寸比在開放面的尺寸更大)、u形或v•形。 再者,凹處之内壁的表面粗糙度為20微米或更小,較佳 為15微米或更小,更佳為10微米或更小,並且一般為〇〇5 微米或更多,如溝槽内壁的一樣。 溝槽的型式可在研磨墊的表面上藉著以具有刀片之切割 機切割而形成。構成刀片的材質不特別受限,但可選自碳 鋼、合金鋼、高速鋼、超硬合金、窯業金屬(cermet)、鎢 鉻鈷合金(stellite)、超高壓力燒結體及其他陶瓷類。可使 用單一刀片、或具有許多刀片的多重刀片單元。 在表面上具有溝槽之研磨層可無切割地、藉著在容器之 容器中形成具有上述溝槽型式的鑄模(例如:金屬鑄模)而 I成,用於反應、注入起始物質基質混合物到容器中、並 且切割之。 在本發明之研磨墊中,彈性係數隨溫度的適當改變可提 供到聚合物基質,因此使得可能獲得抑制刮傷、並且同時 高平坦化的效果。高移除速率除了上述特徵性質之外,可 根據本發明之另一個較佳具體實施例、以含水溶性顆粒均 I05684.doc 02- 1379853 勻分散其中之研磨墊提供。 【實施方式】 實例 下列實例及比較例被提供’以進一步說明本發明。 用於實例及比較例中之研磨墊的組成及評估結果被顯示 於表1中。在表1中顯示組份之比率的圖示單位是質量的份 數。 實例1 100重量伤數的β·環狀糊精(由Bi〇 Research of Yokohama製造,註冊商標為Dexy pead p_1〇〇,平均顆 粒直徑為20微米)為水溶性顆粒,被注入混合器(Kawata MFG Co·,Ltd.製造,註冊商標為 Super Mixer SMZ 3Sp) 中,並且以喷霧器喷入0.5重量份數的胺基丙基三乙氧基 矽烷(Nippon UniCar Co_,Ltd.製造,註冊商標為 Α·1100)5 分鐘’在每秒400轉的攪拌下與上述的水溶性顆粒混合。 然後,攪拌在每秒400轉下再繼續2分鐘。之後,從混合器 中取出之顆粒以在設定在13〇。〇的真空乾燥器加熱乾燥, 直到顆粒的水含量變成5,〇〇〇 ppm或更低,獲得表面以矽 烧偶合劑處理過的β-環狀糊精。 、58重量伤數的4,4-一苯基甲燒二異氰酸醋(Sumika Bayer Urethane Co.,Ltd·製造,註冊商標為Sumijule 44S)被進料 到反應器,5.1重量份數之在分子兩端具有兩個羥基基 團、並且敦量平均分子量650的聚四亞曱基二醇 (Mitsubishi Chemical Corporation 製造,註冊商標為 105684.doc -33- 1379853 PTMG650)及17.3重量份數之具有數量平均分子量25〇的聚 四亞甲基二醇(Mitsubishi Chemical Corporation製造,註冊 商標為PTMG2 50)在60 °C下有攪拌地被添加到反應器,在 9〇°C下、有攪拌地進行反應2小時,並且然後反應產物被 冷卻’獲得異氰酸酯終端的預聚物。此異氰酸酯終端的預 聚物為21重量%之未反應4,4’-二苯基甲烷二異氰酸酯及79 重量%在兩端具有異氰酸酯基團之預聚物的混合物。 80.4重量份數的所得異氰酸酯終端預聚物被進料到搜掉 容器中,並且維持在90°C,14.5重量份數之上述獲得、表 面以石夕烧偶合劑處理過的水溶性顆粒,在每秒2〇〇轉的搜 拌下被添加到預聚物中,並且混合並分散1小時,並且然 後進行真空除泡,獲得含水溶性顆粒分散其中之異氰酸龍 終端的預聚物。 12.6重量份數之在終端具有兩個羥基基團的1,4_雙(|3_羥 基乙氧基)苯(Mitsui Fine Chemicals Inc.製造,註冊商標為 BHEB) ’在1201下、有攪拌的容器中被加熱2小時到熔 化’並且7重量份數之具有三個羥基基團的三甲基醇丙烷 (BASF Japan Ltd.製造,註冊商標TMP)在攪拌下被添加到 熔融產物中’被混合並且溶解1〇分鐘,獲得鏈延伸劑的混 合物。 在120°C下被加熱之19.6重量份數的上述獲得鏈延伸劑 混合物被添加,並且與上述獲得之94.9重量份數之含水溶 性顆粒分散其中的異氰酸酯终端預聚物混合1分鐘,同時 該預聚物在90°C下被加熱’並且在攪拌混合器中攪拌,獲 105684.doc -34· 1379853 得起始物質混合物β 上述的起始物質混合物被注入具有直徑6〇〇毫求且厚度3 毫1之碟形凹洞金屬鑄模中,直到其填滿凹洞並且在 110 C下維持30分鐘,進行聚胺基甲酸酯化反應,並且所 得之鑄k產物從禱模令被移除。再者,所得之禱造產物在 110C之可變溫烘箱(gear 〇ven)中被後固化16小時獲得含 分散水溶性顆粒之聚胺基甲酸酯片狀物,並且具有直徑 600毫米且厚度3毫米。水溶性顆粒對整個片狀物的體積分 數,也就是水溶性顆粒對聚胺基f酸酯基質及水溶性顆粒 之總體積的體積分數為10〇/〇。 所得之片狀物的Shore D硬度為84»該片狀物被切成具 有寬度3毫米、厚度3毫米及長度32毫米的條狀物,要在測 量溫度-20至130°C下、起初負載5〇克、動力偏差0 05。/〇及 頻率10雷得/秒的張力模式中被測量,並且在溫度升高速 率為 5 C/分鐘、使用(Rheometrics,Inc.的)Solids Analyzer RSA-ii動力黏彈性測試儀器。條狀物在3(rc、6〇<t及9(rc 之儲存彈性係數分別為1,895百萬巴斯卡(MPa)、175百萬 巴斯卡及110百萬巴斯卡,在30«c之儲存彈性係數對在60 C之儲存彈性係數的比率為1〇8,並且在3〇 〇c之儲存彈性 係數對在90°C之儲存彈性係數的比率為17.2 ^條狀物的硬 度在其含浸於23°C去離子水24小時之後測量為抗水穩定性 的指標’當其被用來與淤漿接觸的研磨時,片狀物的 Shore D硬度為77 ’其為低於含浸前7點。 具有pitch 2毫米、寬度〇.5毫米及深度1>5毫米的同心圓 105684.doc -35· 1379853 狀溝槽’在片狀物的整個矣; 個表面上形成,不包括片狀物的30 毫米中心部份,並且AL, AA m ts, J. 片狀物的周圍部份使用切割機移除, 除50.8a刀直徑的中心部份之外’並且壓敏雙重塗覆膠帶 (3M Ltd.的442IS)被ϋ定到缺之片狀物溝槽的整個背面。 研磨塾的研磨表現如下被評估。 (1)移除速率及刮傷的存在Water Soluble Particle C Another preferred embodiment of the invention is a polishing pad having an abrasive layer comprising a water soluble particle knives dispersed in the polymer matrix. In this polishing pad 105684.doc • 21 - 1379853, during the conditioning, the water-soluble particles are removed from the polymer matrix when they are in contact with water, or when using a polishing pad, during polishing, on the surface layer of the pad It is excluded from the slurry of the aqueous dispersion. This exclusion occurs when the water-soluble particles are contacted with water or water contained in a slurry to be dissolved in water, or when the water-soluble particles are swollen with water to be gelatinized. Further, this dissolution or expansion occurs not only when it comes into contact with water but also when it comes into contact with an aqueous mixed medium containing a solvent such as methanol. The water-soluble granules have the effect of increasing the dent hardness of the polishing pad and reducing the dent of the polishing bur on the object to be ground, in addition to the effect of forming the pores, by pressurizing the polishing pad (for example: by containing water) Particles 'The Shore D hardness of the abrasive layer of the abrasive crucible of the present invention can be set to preferably 35 or more' more preferably 40 to 95, most preferably 50 to 90 〇 when the Shore D hardness is 35 or more. The pressure to the target to be ground can be large' and thus the removal rate can be improved. Further, the high polishing flatness of the object to be polished can be achieved by the presence of water-soluble particles. Therefore, the water-repellent particles are preferably solid so that they can ensure a sufficiently high depression hardness to the polishing pad. The substance constituting the water-soluble particles is not particularly limited. For example, it is an organic water-soluble particle or an inorganic water-soluble particle. Examples of the substance of the organic water-soluble granule include sugar (polysaccharide such as starch, dextrin, cyclodextrin, lactose, mannitol, etc.), cellulose (e.g., hydroxypropylcellulose, decylcellulose, etc.), Protein, polyvinyl alcohol, polyvinyl tetrahydrofuranone, polyacrylic acid and its salts, polyethylene oxide, water-soluble photosensitive resin, sulfonated polyisoprene and continuous isoprene copolymer Examples of materials for inorganic water-soluble particles 105684.doc • 22-1379853 includes potassium acetate, potassium nitrate, potassium carbonate, potassium hydrogencarbonate, potassium chloride, potassium bromide, potassium phosphate and magnesium nitrate. These water-soluble particles may be used singly or in combination of two or more. The water/capacitive particles have an average particle diameter of preferably from 〇 i to 5 μm, more preferably from 0.5 to 300 μm, still more preferably from iiioo micron, and particularly preferably from 1 to 9 μm. The pores formed by the exclusion of the water-soluble particles are as large as preferably from 〇 to 5 μm, more preferably from 0.5 to 300 μm, still more preferably from 1 to 1 μm, and particularly preferably from 10 to 90 μm. When the average particle diameter of the water-soluble particles is less than 0.1 μm, the pores formed become smaller in size than the abrasive particles used, and thus it is difficult to obtain a polishing pad capable of completing the retention of the slurry. When the average particle diameter is more than 500 μm, the formed pores become too large, so that the mechanical strength and removal rate of the obtained polishing pad are lowered. The amount of the water-soluble particles is preferably from 至5 to 7% by volume, more preferably [to 60% by volume, particularly preferably from 2 to 45% by volume, and the abrasive layer composed of the polymer matrix and the water-soluble particles is 100%. Volume % basis. When the amount of the water-soluble particles is less than 0.5 volume ❶ /. At the time, the holes are not completely formed in the resulting polishing pad, and the removal rate is lowered. When the amount of the water-soluble particles is more than 7% by volume, it may be difficult to completely prevent the water-soluble particles present inside the obtained polishing pad from being swollen or dissolved during the grinding, thereby making it difficult to maintain the hardness and mechanical strength of the polishing pad. Appropriate value. The calculation of the water-soluble particles in parts by weight can be carried out as follows. For example, when a sugar having a specific gravity of about 1.5 is used as a water-soluble particle, and a polyurethane having a specific gravity of about 1.15 after the end of the reaction is used as a polymer matrix, the amount of the water-soluble particles is preferably 〇7. Up to 75.3 wt%, more preferably ^ 3 105684.doc -23- 1379853 to 66.2 wt% 'particularly preferably 2.6 to 51.6 wt%, with a polishing layer of ίο. The weight is based on the basis. When a polyacrylic acid having a specific gravity of about 1.15, a polyvinyltetrahydrofuranone or a polyethylene oxide is used as the water-soluble particles, and a polyurethane having a specific gravity of about 1.15 is used after the reaction is completed, In the case of a polymer matrix, the amount of the water-soluble particles is preferably from 0.5 to 70% by weight. /. More preferably, it is from i to 60% by weight, particularly preferably from 2 to 45% by weight, based on 1% by weight of the abrasive layer. Further, when inorganic water-soluble particles having a specific gravity of about 2 potassium nitrate are used as water-soluble particles, and a polyaminocarboxylic acid having a specific gravity of about 115 after the end of the reaction is used as a polymer matrix, the water-soluble particles are used. The amount is preferably from 0.9 to 80.2% by weight, more preferably from 1 < 7 to 72% by weight, particularly preferably from 3 4 to 58.7 % by weight, based on 100% by weight of the abrasive layer. It is preferred that when it is exposed to the surface layer of the polishing pad, the water-soluble particles must be dissolved only in water, and when it is present inside the polishing pad, it must not absorb moisture or swell, and therefore, the water-soluble particles are preferably At least a portion of the surface has an outer casing for suppressing moisture absorption. The shell can be physically absorbed • attached to water soluble particles, chemically bonded to water soluble particles, or contacted with water soluble particles by physical adsorption and chemical bonding. The outer casing is made of epoxy resin, polyamido resin, polyamide resin, fluorenone resin or coupling agent, and the t纟 is described as being dispersed as a part of the water-soluble one. When the surface of the particles is on the surface, the above effects can be completely obtained. When water-soluble granules are used, the water-soluble granules are preferably first dispersed in the above-mentioned isocyanate terminal amino-based formic acid-based prepolymer A and/or before the mixing of all the starting materials. The chain extender Bf 〇 is to prevent the water-soluble particles from swelling with the starting material solution, and is dissolved in the starting material when dispersed. In the qualitative solution, it is particularly preferable that the water-soluble particles are dispersed in the chain. The extender B has a higher molecular weight isocyanate terminated urethane prepolymer A. Although the dispersion method is not particularly limited, it is preferred that the water-soluble particles are added and dispersed little by little 'and the isocyanate terminated amino acetal prepolymer A or chain extender B (or in separate containers) Both) are stirred in the container to obtain a good dispersion. It is particularly preferred that the water-soluble particles are dispersed by using a double helix mixer capable of obtaining shear. In order to prevent the foam from being contained in the resulting abrasive layer, the defoaming is preferably carried out under reduced pressure during or after the dispersion of the water-soluble particles. Dispersing aids can be used as appropriate. Examples of the dispersion aid include homopolymers, block copolymers modified with an acid anhydride group, a carboxyl group, a hydroxyl group, an epoxy group, a oxazolium group or an amine group, a nonionic surfactant, and a coupling agent. And random copolymers. Mixing and reacting a starting material in which water-soluble particles are dispersed, and a polishing pad made of the polyurethane or polyamine phthalate-urea containing water-soluble particles dispersed therein, by mixing water The soluble particles are obtained by dispersing the starting materials therein, and the synthesis reaction of the polymer matrix is the same as the mixing and solidification of the starting materials (the isocyanate terminal urethane prepolymer A and the chain extender B). In the above manner, except that the starting material (prepolymer A, chain extender b or both other additives) in which the water-soluble particles prepared by the above method are dispersed may be used in addition to the components of the above components. Addition to the polymer matrix and/or water-soluble particles is limited to not impair the effects of the present invention. 105684.doc -25- 1379853 is included in the abrasive layer of the polishing pad of the present invention, which must be polymerized. The substrate is added to the starting material prior to formation.. Abrasive pad The abrasive layer of the polishing pad of the present invention is pre-polymerized by a mixture of starting materials (isocyanate terminal urethane) And a chain extender B), or obtained by reacting a solution of a starting material mixture containing water-soluble particles dispersed, for example, in the above-described method in a metal mold. The abrasive layer of the polishing pad of the present invention is characterized by: When the temperature is raised by the frictional heat generated by the extreme grinding conditions or the frictional heat generated by the excessive pressure of the rough foreign matter, the elastic modulus is lowered to an appropriate value. The injury can slow down the target to be ground. The excess pressure, thereby reducing the modulus of elasticity (softening), is avoided. By suppressing excessive reduction in the modulus of elasticity at temperature changes, the flattening behavior during grinding can be improved. To achieve this appropriate change in the modulus of elasticity with temperature. , the polishing layer is at 30. (: storage elastic coefficient) ^ is at (10) its E · ratio is in the range of 2 to 15, preferably 3 to 1 〇, and at 3 〇 < t E' pair The ratio of E at 90 ° C is in the range of 4 to 20, preferably 5 to 15. The storage elastic modulus E' must be understood as: when having a strip having a width of 3 mm, a thickness of 3 mm and a length of 32 mm Object is taken from the sheet It was cut out and measured at a test temperature of -20 to 13 (TC, initial load 50 g, dynamic deviation 〇〇 5%, and frequency 10 rad/sec), and at a temperature increase rate of 5. (: / min, when using a commercially available dynamic viscoelasticity tester, it is a value at 30 ° C or 60 ° C. The abrasive layer may constitute at least a portion of the abrasive surface of the polishing pad. The composition is preferably At least 50% or more of the abrasive surface, more preferably at least 8 〇 0 / 〇 or 105684. doc -26 - 1379 853 more 'extra good is at least 90% or more. The entire abrasive surface may be composed of an abrasive layer. The portion outside the layer is, for example, the portion of the window used to extract the end point by the optical end-point detector. The portion of the window is 0.1% or more optically transmissive at a wavelength of 1 〇〇 to 3, _ nm. More, preferably 2% or more of the material is formed, or is made of a material having a wavelength of 100 to 3, 〇〇〇 nanometer having an overall optical transmission of 0.1% or more, preferably 2% or more. And the thickness is 2 mm. Further, the abrasive layer of the polishing pad may be a single layer or a composite sheet containing another layer. In the case of a composite panel, the abrasive layer is a layer that forms an abrasive surface in the composite panel, and the layer other than the abrasive layer is, for example, a support layer disposed on a surface opposite to the abrasive surface of the abrasive layer and used for bonding support The bonding layer of the layer and the abrasive layer together. The above support layer is a layer for supporting the abrasive layer on the back side. Although the characteristic properties of the support layer are not particularly limited, the support layer is preferably softer than the abrasive layer. When the mat is a soft support layer, if the abrasive layer is, for example, 5 mm or less thin, it may be possible to prevent the polishing layer from rising during polishing or the surface of the polishing layer from being bent, so that there may be stable grinding. The hardness of the support layer is preferably 90 Å/〇 or less, and the hardness of the abrasive layer is more preferably 80% or less, particularly preferably 70% or less, and is usually 10. /. Or lower. The Shore D hardness of the support layer is preferably 7 Å or less, more preferably 60 or less, particularly preferably 50 or less, and is usually 1 or less. The floor can be foamed or unfoamed. The planar shape of the support layer is not particularly limited' and may be the same or different from the abrasive layer. The planar shape of the support layer is 105684.doc -27· 1379853. The shape may be a ring shape or a polygonal shape, for example, a quadrangle. The thickness thereof is not particularly limited, but is preferably from 0.1 to 5 mm, more preferably from 0.5 to 2 mm. When the polishing layer.* has a window portion that detects the end point by the optical endpoint detector, the window material has a similar shape or the same shape without blocking the passage of light through the window portion or cutting off the light. The abrasive layer can be formed without a window portion. The material constituting the support layer is not limited by (4). It is preferred to use an organic substance because it is easily cast into a predetermined shape and property and can provide appropriate elasticity. Various polymers can be used as the organic substance. The organic substance constituting the support layer may be a crosslinked polymerized ruthenium, a still crosslinked polymer, or a non-crosslinked polymer. The support layer may be composed of a single layer or multiple layers. Further, the support layer and the polishing layer may be directly combined by heat fusion or by the above-mentioned bonding layer. The bonding layer is a cured layer of an adhesive or a layer made of a pressure-sensitive adhesive such as an adhesive tape. The shape of the polishing pad of the present invention is not particularly limited, and may be in the form of a dish, a belt, or a drum. Preferably, it can be selected as appropriate according to the grinding machine. The size of the polishing pad before use is not particularly limited. In the case of a dish-shaped polishing pad, the diameter thereof is preferably from 0.5 to 500 cm, more preferably from 1 to 25 mm, particularly preferably from 20 to 2 cm, and its thickness is preferably greater than 〇1. Millimeter and 100 mm or less, plus 1 to 10 mm. The grinding process in which this polishing pad is used is not particularly limited. For example: The polishing pad can be suitably used in the STI process (shallow trench isolation process) in the polishing of semiconductor wafers, used to form a damascene process by gossip or wire, used to form by A. Bu-Cu or W-made vias 105684.doc -28- 1379853 Via plug embedding process, dual-injection process for simultaneously forming metal lines and via plugs, grinding interface buffer layer ( The process of insulating films (such as oxide film, low-k or BPSG), the process of grinding nitride films (such as TaN or TiN), and the process of grinding polyfluorene or single crystal germanium. Open grooves and/or recesses may be formed on the abrasive surface of the polishing pad. The grooves and/or recesses are used to retain the slurry supplied during grinding and are more evenly distributed to the abrasive surface. It is also used as a temporary retention of waste such as powder and used slurry produced by grinding. And it becomes a discharge path for discharging waste to the outside. The shape of the groove is not particularly limited. It can be a wheel, a grid, a radiator and/or a spiral. The planar shape of the wheel groove is not particularly limited, and may be a circle such as a triangle, a quadrangle or a hexagonal polygon, or an ellipse. The number of grooves formed on the polishing pad is preferably two or more. Although the arrangement of the grooves is not particularly limited, the grooves may be arranged concentrically or non-concentrically, or a plurality of wheel grooves may be surrounded by a single __ wheel groove in the inner portion of the grinding surface. In addition to these, it is preferred that the grooves are arranged concentrically. More preferably, a plurality of annular grooves are arranged concentrically. A poem with annular grooves arranged concentrically, other grindings superior to the above functions. When the annular grooves are arranged concentrically, they are excellent in these functions and are also easy to be single-continuous The grooves, or two or more discontinuous grooves, may form a lattice. The planar shape of the grid pattern is not particularly limited, and may be polygonal: the poly (four) pattern may be a quadrangle 'such as a square, a rectangle, a trapezoidal diamond, a dih, a pentagon or a hexagon. 105684.doc -29- 1379853 Radial grooves are made up of a number of grooves extending from the center of the grinding bowl to the surrounding. The groove extends from the central portion into a straight line, a chess shape or a combination thereof. Although the groove may or may not reach the end of =, at least it - preferably reaches the surrounding end, i.e. the side of the crucible. For example, a plurality of grooves may be formed by a plurality of linear grooves extending from the central portion to the periphery, at least one of which may reach the side of the crucible, or a plurality of grooves may be formed by a plurality of linear grooves extending from the center portion to the periphery. And a plurality of linear grooves extending from a central portion and a peripheral portion to a surrounding portion, at least - which can reach the side of the pad. Many grooves can form a pair of parallel linear grooves. A spiral continuous groove may be formed, or two spiral grooves different in direction from each other may be formed. Further, two spiral grooves which are the same in the direction may be formed or three or more spiral grooves which are the same or different in the direction may be formed. The size of the above groove is not particularly limited. For example, the width of the groove is preferably 〇1 mm or more, more preferably, more preferably 〇2 to 3 mm' is particularly preferably from 0.5 to 1 mm, and it is difficult to form a width or minimum. Grooves smaller than 0. 1 mm in size. The depth of the groove is preferably 〇 1 mm or more, more preferably 0.3 to 2.5 mm, still more preferably a millicalium, particularly preferably 1.3 to 2 mm. When the depth of the groove is less than 〇1 mm, the service life of the grinding crucible tends to become too short. Further, the interval between the grooves (the minimum distance between adjacent portions in the radiation direction of the spiral groove) is preferably 0.05 mm or more, more preferably 〇〇5 to 1 mm, More preferably (Μ to 1 mm, especially preferably 55 to 2 mm. It is difficult to form a groove with a minimum distance of 684.05 mm of 105684.doc -30· 1379853. The width and proximity of the groove The pitch of the sum of the distances between the grooves is preferably 〇15 mm or more, more preferably 〇'15 to 1 () 5 mm, more preferably 〇 to 13 mm, particularly preferably to 2.2. The preferred range can be combined. For example, the groove preferably has a width of 0" mm or more, a depth of 〇" mm or more, and a minimum distance of 〇. 〇 5 mm or more. The ground width is n5 mm, the depth is 〇.3 to η mm and the minimum distance is from 0.05 to 1 〇〇, more preferably the width is 0.2 to 3 mm, the depth is m.2 mm and the minimum distance is 〇1. To 1 inch: meters, especially good for width 0.5 Μ milli#, depth w 3 to 2 mm and minimum distance of 0.5 to 2 mm. Furthermore, the surface of the inner wall of the groove The roughness is preferably 2 μm or less, more preferably 15 μm or less, preferably 1 μm or less, and is generally 5 μm or more. When the surface roughness is preferably 2 μm or less, scratching during grinding can be effectively avoided. This surface roughness must be understood as the value before the use of the polishing pad of the present invention. "The surface roughness is preferably 20 μm or more. In the hour, large changes do not exist. When large changes do not exist, for example, extra large protrusions of debris generated when grooves are formed, the results of scratching during grinding are excluded. Furthermore, scratches may occur during grinding. Pressure or frictional heat, by foreign matter formed by compression, or by interaction between the protrusions and powders produced by grinding, or solids contained in the slurry. The protrusions can be excluded during trimming The same inconvenience is caused. Further, when the surface roughness is preferably 20 μm or less, the scratch can be avoided by 105684.doc 1379853, and the function of the groove, particularly the function of distributing the slurry to the polished surface, and Discharge waste to The outer function is effectively obtained. The planar shape of the above recess is not particularly limited, for example, it may be a ring shape or an empire shape such as a triangle %, a quadrangle or a pentagon, or an ellipse. It is not particularly limited. For example, it may be a shape formed by a flat side surface and a bottom surface (the dimensions in the transverse direction of the open surface and the bottom surface may be the same, the size of the open surface may be larger than the size of the bottom surface, or The size of the bottom surface is larger than that of the open surface, u-shaped or v-shaped. Further, the inner surface of the recess has a surface roughness of 20 μm or less, preferably 15 μm or less, more preferably 10 microns or less, and typically 〇〇 5 microns or more, as is the inner wall of the trench. The pattern of grooves can be formed on the surface of the polishing pad by cutting with a cutter having a blade. The material constituting the blade is not particularly limited, but may be selected from the group consisting of carbon steel, alloy steel, high speed steel, super hard alloy, cermet metal, stellite, ultra high pressure sintered body, and other ceramics. A single blade or multiple blade units with many blades can be used. An abrasive layer having a groove on the surface may be formed without a cutting by forming a mold having the above-described groove pattern (for example, a metal mold) in a container of the container for reacting and injecting the starting material matrix mixture into In the container, and cut it. In the polishing pad of the present invention, an appropriate change in the modulus of elasticity with temperature can be supplied to the polymer matrix, thus making it possible to obtain an effect of suppressing scratching and at the same time, high planarization. In addition to the above-described characteristic properties, the high removal rate can be provided in accordance with another preferred embodiment of the present invention in which the polishing pad is uniformly dispersed with water-soluble particles I05684.doc 02-1379853. [Examples] Examples The following examples and comparative examples are provided to further illustrate the present invention. The compositions and evaluation results of the polishing pads used in the examples and comparative examples are shown in Table 1. The graphical unit showing the ratio of components in Table 1 is the fraction of mass. Example 1 100 weight-damaged β·cyclodextrin (manufactured by Bi〇 Research of Yokohama, registered trademark Dexy pead p_1〇〇, average particle diameter 20 μm) was a water-soluble granule, which was injected into a mixer (Kawata MFG) Manufactured by Co., Ltd. under the registered trademark of Super Mixer SMZ 3Sp), and sprayed with 0.5 parts by weight of aminopropyltriethoxydecane (manufactured by Nippon UniCar Co., Ltd.) under the registered trademark. Α·1100) 5 minutes 'mixed with the above water-soluble granules under stirring at 400 rpm. Then, the stirring was continued for 2 minutes at 400 rpm. Thereafter, the particles taken out from the mixer were set at 13 Torr. The vacuum dryer of the crucible was dried by heating until the water content of the pellet became 5, 〇〇〇 ppm or less, and a β-cyclodextrin having a surface treated with a smoldering coupler was obtained. 58 weight-injured 4,4-phenylene acetonate diisocyanate (manufactured by Sumika Bayer Urethane Co., Ltd., registered trademark Sumijule 44S) was fed to the reactor, and 5.1 parts by weight was Polytetradecylene diol having two hydroxyl groups at both ends of the molecule and having an average molecular weight of 650 (manufactured by Mitsubishi Chemical Corporation, registered trademark 105684.doc -33-1379853 PTMG650) and 17.3 parts by weight Polytetramethylene glycol (manufactured by Mitsubishi Chemical Corporation, trade name: PTMG2 50) having an average molecular weight of 25 Å was added to the reactor with stirring at 60 ° C, and the reaction was carried out at 9 ° C under stirring. 2 hours, and then the reaction product was cooled 'to obtain an isocyanate terminated prepolymer. The isocyanate terminated prepolymer was a mixture of 21% by weight of unreacted 4,4'-diphenylmethane diisocyanate and 79% by weight of a prepolymer having isocyanate groups at both ends. 80.4 parts by weight of the obtained isocyanate terminal prepolymer was fed into the search container, and maintained at 90 ° C, 14.5 parts by weight of the above-obtained water-soluble particles treated with the surface of the catalyst, at The mixture was added to the prepolymer at a rate of 2 Torr per second, and mixed and dispersed for 1 hour, and then vacuum defoamed to obtain a prepolymer containing a terminal of isocyanate in which water-soluble particles were dispersed. 12.6 parts by weight of 1,4-bis(|3_hydroxyethoxy)benzene having a hydroxyl group at the terminal (manufactured by Mitsui Fine Chemicals Inc., registered trademark BHEB) 'with stirring at 1201 The vessel was heated for 2 hours to melt' and 7 parts by weight of trimethylolpropane (manufactured by BASF Japan Ltd., registered trademark TMP) having three hydroxyl groups was added to the molten product under stirring' was mixed And dissolved for 1 minute to obtain a mixture of chain extenders. 19.6 parts by weight of the above-obtained chain extender mixture heated at 120 ° C was added, and mixed with the above-obtained 94.9 parts by weight of the isocyanate terminal prepolymer in which the water-soluble particles were dispersed, for 1 minute, while the pretreatment The polymer was heated at 90 ° C and stirred in a stirring mixer to obtain 105684.doc -34· 1379853 to obtain a starting material mixture β. The above starting material mixture was injected with a diameter of 6 μm and a thickness of 3 In the dish-shaped recessed metal mold of the millimeter, until it was filled with the pit and maintained at 110 C for 30 minutes, the polyurethaneization reaction was carried out, and the obtained cast k product was removed from the prayer mold. Further, the obtained Prayer product was post-cured in a 110 C variable temperature oven (gear 〇ven) for 16 hours to obtain a polyurethane sheet containing dispersed water-soluble particles, and having a diameter of 600 mm and a thickness of 3 Millimeter. The volume fraction of the water-soluble particles to the entire sheet, that is, the volume fraction of the water-soluble particles to the total volume of the polyamino-based acid ester matrix and the water-soluble particles was 10 Å/Å. The obtained sheet had a Shore D hardness of 84». The sheet was cut into strips having a width of 3 mm, a thickness of 3 mm, and a length of 32 mm, at a measurement temperature of -20 to 130 ° C, at the initial load. 5 grams, power deviation 0 05. / 〇 and the frequency 10 Reid / sec tension mode was measured, and the temperature rise rate of 5 C / min, using (Rheometrics, Inc.) Solids Analyzer RSA-ii dynamic viscoelastic test instrument. The strips are at 3 (rc, 6 〇 < t and 9 (rc have a storage elastic modulus of 1,895 million Baska (MPa), 175 million Baska and 110 million Baska, respectively). The ratio of the storage elastic modulus of 30«c to the storage elastic modulus at 60 C is 1〇8, and the ratio of the storage elastic modulus at 3〇〇c to the storage elastic modulus at 90°C is 17.2^ The hardness was measured as an index of water resistance stability after it was immersed in deionized water at 23 ° C for 24 hours. When it was used for grinding in contact with the slurry, the Shore D hardness of the sheet was 77 ' which was lower than 7 points before impregnation. Concentric circles with pitch 2 mm, width 〇5 mm and depth 1> 5 mm 105684.doc -35· 1379853 The groove is formed on the entire surface of the sheet; not included The 30 mm center portion of the sheet, and the surrounding portion of the sheet, AL, AA m ts, J., is removed using a cutter, except for the center portion of the 50.8a knife diameter' and pressure sensitive double coating The tape (442IS of 3M Ltd.) was set to the entire back surface of the missing sheet groove. The grinding performance of the grinding burr was evaluated as follows. (1) Removal rate and The existence of injury
Si02固體薄膜半導體晶圓(Α_η⑽w•製造,具有直徑 200毫米及厚度1,_毫微米的熱氧化物晶圓)在下列條件下 被研磨2分鐘’以評估移除速率、移除速率的晶圓内不均 勻(WIWNU)及到傷的存在。移除速率以光學薄膜厚度尺 在49個點、除了晶圓5毫米周圍部分之外,在沿晶圓中心 部份之直徑的方向研磨之前及之&、從藉著測量薄膜厚度 所獲得之薄膜厚度差的平均值計算。移除速率的晶圓内不 均勻性(WIWNU)從上述49個點的測量值計算,以(標準差 σ/平均移除速率xl〇0)表示為基礎。刮傷的數目以(KLA Tencor Co. Ltd.的)K235 1晶圓偵測檢查機測量。在研磨之 前,該墊的表面使用(3M Ltd.的A-160)鑽石修整器粗糙化 (修整)20分鐘,在如研磨的相同條件下,除了使用具有流 速1,500毫升/分鐘的行進晶圓之外。修整與晶圓的研磨同 時進行’而淤漿在研磨的評估期間流動。Si02 solid thin film semiconductor wafer (manufactured by Αηη (10)w•, with a diameter of 200 mm and a thickness of 1, _nm of thermal oxide wafer) was ground for 2 minutes under the following conditions to evaluate the removal rate, removal rate of the wafer Inhomogeneity (WIWNU) and the presence of injury. The removal rate is obtained by measuring the thickness of the film at an angle of 49 dots, except for the peripheral portion of the wafer 5 mm, in the direction of the diameter of the center portion of the wafer. The average value of the film thickness difference is calculated. The in-wafer inhomogeneity (WIWNU) of the removal rate is calculated from the above-mentioned measured values of 49 points, based on (standard deviation σ / average removal rate xl 〇 0). The number of scratches was measured by a K235 1 wafer inspection inspection machine (KLA Tencor Co. Ltd.). Prior to grinding, the surface of the mat was roughened (trimmed) using a (3M Ltd. A-160) diamond dresser for 20 minutes, except for running crystals having a flow rate of 1,500 ml/min under the same conditions as grinding. Beyond the circle. The trimming is performed simultaneously with the grinding of the wafer while the slurry flows during the evaluation of the grinding.
淤漿:CMS1101 (JSR Corporation製造,含氧化矽為研磨 顆粒)的3倍稀釋; 化學機械研磨機:(Applied Materials,Inc·的)MIRRA 淤漿流速:200(毫升/分鐘) 105684.doc -36- 丄3 . 、.日日圓研磨定位環(retainer ring)/薄膜=400/250 (克/立方公分) ^整負載:350 (克/立方公分) 平臺的解析:63 (每秒轉) 研磨頭的解析:57 (每秒轉) 修整器的解析:63 (每秒轉) 修整器掃磨型式:12掃磨/分鐘 果疋.移除速率為216毫微米/分鐘,移除速率的晶圓内 不句句i± (WIWNU)為6.4%,並且刮傷的數目為2136。 (2)平坦度的評估 當在表面上具有Si〇2薄臈型式之半導體晶圓型式突出物 的起初程度差異約毫微米(Skw Associated Co.,Ltd製 造’註冊商標為SKW_7)時,起初程度差異約8〇〇毫微米的 型式在上述研磨條件下被研磨,在Si〇2薄膜型式之凹處中 之心〇2薄膜的研磨份量被採用為平坦度。在此數值較小 時’該型式晶圓的平坦度變得較高。si(>2薄膜厚度以測量 光學薄膜厚度尺在研磨之前及之後藉著薄膜厚度計算。結 果是:平坦度為123毫微米》 實例2至10及比較例1至3 ,除了使用之起始物質及鑄造條件如表丨中顯示地改變之 外’以如實m中相同的方式獲得研磨塾。片狀物的物理 性質及該墊的研磨表現以如實例丨中相同的方式評估’並 且顯示於表1中。 比較例4及5 105684.doc -37- 1379853 除丁使用商業可獲得之胺基甲酸酯預聚物(在比較例4中 為Adiprene LFH120及在比較例5中為Adiprene L315 (皆由 UNIROYAL CHEMICAL Co.,Inc.製造))做為異氰酸酯終端 之預聚物、並且其他起始物質及鑄造條件如表1中顯示地 改變之外,以如實例1中相同的方式獲得研磨墊。片狀物 的物理性質及該墊的研磨表現以如實例1中相同的方式評 估,並且顯示於表1中。 比較例6 片狀物的物理性質藉著使用具有無溝槽之商業可獲得的 單層胺基曱酸醋塾(Rohn & Haas Electronic Materials Co., Ltd.之IC 1000)評估,並且研磨表現藉著使用有同心圓狀溝 槽之商業可獲得的多層胺基曱酸酯墊(Rohn & Haas Electronic Materials Co·,Ltd.之 IC1000 (K-溝槽)/Suba400) 評估。評估結果顯示於表1中。 105684.doc •38· 1379853 •·Slurry: CMS1101 (manufactured by JSR Corporation, containing cerium oxide as abrasive particles) 3-fold dilution; Chemical mechanical mill: (Applied Materials, Inc.) MIRRA Slurry flow rate: 200 (ml/min) 105684.doc -36 - 丄3 . . . Japanese yen grinding retainer ring (retainer ring) / film = 400 / 250 (g / cubic centimeter) ^ full load: 350 (g / cm ^ 3) Platform analysis: 63 (per second) grinding head Resolution: 57 (revolutions per second) Dresser resolution: 63 (revolutions per second) Dresser sweep pattern: 12 sweeps per minute. Removal rate of 216 nm/min, wafer removal rate The internal sentence i± (WIWNU) is 6.4%, and the number of scratches is 2136. (2) Evaluation of flatness When the initial degree difference of the semiconductor wafer type protrusion having the Si〇2 thin-type type on the surface is about nanometer (Sww Associated Co., Ltd.'s registered trademark is SKW_7), the initial degree The pattern having a difference of about 8 nm was ground under the above-mentioned grinding conditions, and the amount of the polishing of the core 2 film in the recess of the Si〇2 film type was adopted as the flatness. When the value is small, the flatness of the type of wafer becomes higher. Si (>2 film thickness to measure the optical film thickness gauge by film thickness before and after grinding. The result is: flatness of 123 nm. Examples 2 to 10 and Comparative Examples 1 to 3, except for the start of use The substance and the casting conditions were changed as shown in the table. 'The grinding enthalpy was obtained in the same manner as in the m. The physical properties of the sheet and the abrasive behavior of the mat were evaluated in the same manner as in the example '' and shown in In Table 1. Comparative Examples 4 and 5 105684.doc -37- 1379853 A commercially available urethane prepolymer (Adiprene LFH120 in Comparative Example 4 and Adiprene L315 in Comparative Example 5) was used in addition to the butyl group. The polishing pad was obtained in the same manner as in Example 1 except that the prepolymer of the isocyanate terminal was used as the prepolymer of the isocyanate terminal, and the other starting materials and casting conditions were changed as shown in Table 1. The physical properties of the sheet and the abrasive behavior of the mat were evaluated in the same manner as in Example 1 and are shown in Table 1. Comparative Example 6 The physical properties of the sheet were commercially available by using a groove-free commercial Single Amino bismuth citrate (ICR 1000 from Rohn & Haas Electronic Materials Co., Ltd.) was evaluated and the performance was demonstrated by the use of a commercially available multilayer amine phthalate pad (Rohn) with concentric circular grooves. & Evaluation of IC1000 (K-Groove)/Suba400) by Haas Electronic Materials Co., Ltd. The results of the evaluation are shown in Table 1. 105684.doc •38· 1379853 •·
Ex. 8 1 1 1 45.9 1 1 (850) 40.6 1 1 Ex. 7 1 1 1 45.9 1 1 (850) 40.6 1 1 Ex. 6 1 1 1 45.9 1 1 (850) 40.6 1 1 Ex. 5 1 42.5 22.9 1 1 1 (2300) 27.9 1 1 Ex. 4 1 13.7 41.1 1 1 1 (1500) 34.3 1 1 Ex. 3 1 1 1 45.9 1 1 (850) 40.6 1 1 Ex. 2 1 1 1 1 16.2 12.5 (476) 56.3 1 1 Ex. 1 1 1 1 1 17.3 (341) 00 1 <異氰酸酯終端之胺基曱酸酯預聚物A> PTMG3000 (數量平均分子量3000) PTMG1000 (數量平均分子量1000) PTMG850 (數量平均分子量850) PIMG650 (數量平均分子量650) PTMG250 (數量平均分子量250) 化合物Y的數量平均分子量 MDI (二苯基曱烷二異氰酸酯) 商業可獲得之預聚物Adiprene LFH120 商業可獲得之預聚物Adiprene L315 ¥駟:.X3 105684.doc -39- 1379853 • · (Ϊ)Ι <Ex. 8 1 1 1 45.9 1 1 (850) 40.6 1 1 Ex. 7 1 1 1 45.9 1 1 (850) 40.6 1 1 Ex. 6 1 1 1 45.9 1 1 (850) 40.6 1 1 Ex. 5 1 42.5 22.9 1 1 1 (2300) 27.9 1 1 Ex. 4 1 13.7 41.1 1 1 1 (1500) 34.3 1 1 Ex. 3 1 1 1 45.9 1 1 (850) 40.6 1 1 Ex. 2 1 1 1 1 16.2 12.5 ( 476) 56.3 1 1 Ex. 1 1 1 1 1 17.3 (341) 00 1 <isocyanate terminated amino phthalate prepolymer A> PTMG3000 (quantitative average molecular weight 3000) PTMG1000 (quantitative average molecular weight 1000) PTMG850 (quantity Average molecular weight 850) PIMG650 (quantitative average molecular weight 650) PTMG250 (quantitative average molecular weight 250) Number average molecular weight of compound Y MDI (diphenylnonane diisocyanate) Commercially available prepolymer Adiprene LFH120 Commercially available prepolymer Adiprene L315 ¥驷:.X3 105684.doc -39- 1379853 • · (Ϊ)Ι <
Ex. 8 00 Ex. 7 00 S Ex. 6 00 S Ex. 5 CN Η Ex. 4 rn — v〇 Ex.3 00 Ex. 2 10.1 〇\ 寸· Ex. 1 〇 12.6 <鏈延伸劑B> (三官能基鏈延伸劑) 三官能基PPG Uniol TG330 (數量平均分子量330) 三甲基醇丙院TMP (分子量134) (二官能基鏈延伸劑) PIMG650 (數量平均分子量650) 1,4-雙(羥基乙氧基)苯(分子量19S) 1,6-己烧二醇(分子量118) 3,3·-二氣~4,4'_二胺基二苯基甲烧(分子量267) 〈固化觸媒〉 2-曱基三乙烯二胺[Me-DABCO] Adecastab BT11 f# 駟:dw 105684.doc •40- 1379853 *製)I啭 • · C. Ex. 6 IC1000 C. Ex. 5 ... 1 1 1 1 1 1 未知 1 1 1- 79.3 C. Ex. 4 . 1 1 1 1 1 1 未知 1 86.7 1 C. Ex. 3 1 1 1 1 1 23.1 (250) 46.3 1 1 C. Ex. 2 1 1 1 1 Η ui 11.6 (476) 52.3 1 1 C. Ex. 1 1 1 1 1 in 11.6 (476) 52.3 1 1 Ex. 10 1_ 1 1 1 確 f i in 11.6 (476) 52.3 1 1 Ex. 9 1 1 1 45.9 1 1 (850) 40.6 1 ' <異氰酸酯終端之胺基曱酸酯預聚物A> PTMG3000 (數量平均分子量3000) PTMG1000 (數量平均分子量1000) PTMG850 (數量平均分子量850) PTMG650(數量平均分子量650) PTMG250 (數量平均分子量250) 化合物Y的數量平均分子量 MDI (二苯基曱烷二異氰酸酯) 商業可獲得之預聚物Adiprene LFH120 商業可獲得之預聚物Adiprene L315 ί#^^:·ΧΗ·υ苳駟:.Χ3 105684.doc -41 · 1379853 «變)I硌 • · C. Ex. 6 C. Ex. 5 20.7 C. Ex. 4 CN <N 11.1 0.015 C. Ex. 3 13.2 17.4 C.Ex.2 κη in in 〇 C. Ex. 1 m 卜 Ex. 10 in in — Ex. 9 00 5 <鏈延伸劑8> (三官能基鏈延伸劑) 三官能基PPG Uniol TG330 (數量平均分子量330) 三曱基醇丙烧TMP(分子量134) (二官能基鏈延伸劑) PTMG650(數量平均分子量650) 1,4-雙(羥基乙氧基)苯(分子量19S) 1,6-己烧二醇(分子量118) 3,3’-二氯-4,4’-二胺基二苯基曱烷 (分子量267) 〈固侧媒〉 2-甲基三乙烯二胺[Me^DABCO] Adecastab BT11 f杳銻玉:.X3 ·0 i# 駟:.xw 105684.doc -42- 1379853 • · *ϋEx. 8 00 Ex. 7 00 S Ex. 6 00 S Ex. 5 CN Η Ex. 4 rn — v〇Ex.3 00 Ex. 2 10.1 〇\ Inch · Ex. 1 〇12.6 < Chain Extender B> (Trifunctional chain extender) Trifunctional PPG Uniol TG330 (number average molecular weight 330) Trimethylol propyl TMP (molecular weight 134) (difunctional chain extender) PIMG650 (quantitative average molecular weight 650) 1,4- Bis(hydroxyethoxy)benzene (molecular weight 19S) 1,6-hexane diol (molecular weight 118) 3,3·-dioxin~4,4'-diaminodiphenylmethane (molecular weight 267) Curing Catalyst> 2-Mercaptotriethylenediamine [Me-DABCO] Adecastab BT11 f# 驷:dw 105684.doc •40- 1379853 *System) I啭• · C. Ex. 6 IC1000 C. Ex. 5 .. 1 1 1 1 1 1 Unknown 1 1 1- 79.3 C. Ex. 4 . 1 1 1 1 1 1 Unknown 1 86.7 1 C. Ex. 3 1 1 1 1 1 23.1 (250) 46.3 1 1 C. Ex. 2 1 1 1 1 Η ui 11.6 (476) 52.3 1 1 C. Ex. 1 1 1 1 1 in 11.6 (476) 52.3 1 1 Ex. 10 1_ 1 1 1 Indeed fi in 11.6 (476) 52.3 1 1 Ex. 9 1 1 1 45.9 1 1 (850) 40.6 1 ' <isocyanate Amino phthalate prepolymer A> PTMG3000 (quantitative average molecular weight 3000) PTMG1000 (quantitative average molecular weight 1000) PTMG850 (quantitative average molecular weight 850) PTMG650 (quantitative average molecular weight 650) PTMG250 (quantitative average molecular weight 250) Compound Y A number average molecular weight MDI (diphenyldecane diisocyanate) Commercially available prepolymer Adiprene LFH120 Commercially available prepolymer Adiprene L315 ί#^^:·ΧΗ·υ苳驷:.Χ3 105684.doc -41 · 1379853 «变变I硌• · C. Ex. 6 C. Ex. 5 20.7 C. Ex. 4 CN <N 11.1 0.015 C. Ex. 3 13.2 17.4 C.Ex.2 κη in in 〇C. Ex 1 m 卜Ex. 10 in in — Ex. 9 00 5 <chain extender 8> (trifunctional chain extender) trifunctional PPG Uniol TG330 (number average molecular weight 330) tridecyl alcohol propyl alcohol TMP ( Molecular weight 134) (difunctional chain extender) PTMG650 (number average molecular weight 650) 1,4-bis(hydroxyethoxy)benzene (molecular weight 19S) 1,6-hexane diol (molecular weight 118) 3,3' -dichloro-4,4'-diaminodiphenyl decane (molecular weight 267) <solid side medium> 2-methyltriethylenediamine [Me^DABCO] Adecastab BT11 f杳锑玉:.X3 ·0 i# 驷:.xw 105684.doc -42- 1379853 • · *ϋ
Ex. 4 (100%) (39.4%) (172.9) (8.67) 32.4 0.162 32.6 (20.0%) 110〇C*30 分鐘 110°C*16 小時 Ex. 3 (100%) (35.6%) (175.4) (4.84) 14.4 0.072 14.5 (10.0%) 110。。*30 分鐘 110°C*16 小時 Ex. 2 (100%) (67.3%) (155.1) (3.07) 14.4 0.072 14.5 (10.0%) 11(TC*30 分鐘 110°C*16 小時 Ex. 1 (100%) (35.7%) 1_ (175.3) (1.95) 14.4 0.072 14.5 (10.0%) 110。。*30 分鐘 110°C*16 小時 具有數量平均分子量300或更少之鏈延伸劑的份量 (重量%) 三官能基鏈延伸劑的份量(重量%) 鏈延伸劑B的數量平均分子量 Y之數量平均分子量對B之數量平均分子量的比率 <水溶性顆粒〇 β-環狀糊精 (平均顆粒直徑20微米) γ-胺基丙基三乙氧基石夕烧Α1100 以矽烧偶合劑處理的β -環狀糊精 水溶性顆粒的份量(體積%) 〈鑄造條件〉 在從鎮模移除之前的條件 後固化的條件 f# 駟:·Χ3 105684.doc -43· 1379853 (置I <• ·Ex. 4 (100%) (39.4%) (172.9) (8.67) 32.4 0.162 32.6 (20.0%) 110〇C*30 minutes 110°C*16 hours Ex. 3 (100%) (35.6%) (175.4) (4.84) 14.4 0.072 14.5 (10.0%) 110. . *30 minutes 110°C*16 hours Ex. 2 (100%) (67.3%) (155.1) (3.07) 14.4 0.072 14.5 (10.0%) 11(TC*30 minutes 110°C*16 hours Ex. 1 (100 %) (35.7%) 1_ (175.3) (1.95) 14.4 0.072 14.5 (10.0%) 110.*30 minutes 110°C*16 hours The amount of chain extender with a weight average molecular weight of 300 or less (% by weight) The amount of the trifunctional chain extender (% by weight) The ratio of the number average molecular weight of the chain extender B to the number average molecular weight of B. <Water-soluble particles 〇β-cyclodextrin (average particle diameter 20微米-Aminopropyltriethoxy saponin 1100 The amount of the water-soluble granules of the β-cyclodextrin treated with the oxime coupling agent (% by volume) <Casting conditions> Conditions before removal from the mold Post-cure conditions f# 驷:·Χ3 105684.doc -43· 1379853 (I <• ·
Ex. 8 (100%) (35.6%) (175.4) (4.84) 1 1 1 1 110〇C*30 分鐘 110°C*16 小時 Ex. 7 (100%) (35.6%) (175.4) (4.84) 240.8 1.204 CN (65.0%) 11(TC*30 分鐘 110°C*16 小時 Ex. 6 (100%) (35.6%) (175.4) (4.84) rn 0.006 rn (1.0%) 110〇C*30 分鐘 110°C*16 小時 Ex. 5 (100%) (62.7%) (128.2) (17.94) 55.6 0.278 55.9 (30.0%) 110〇C*30 分鐘 110°C*16 小時 具有數量平均分子量300或更少之鏈延伸劑的份量 (重量%) 三官能基鏈延伸劑的份量(重量%) 鏈延伸劑B的數量平均分子量 Y之數量平均分子量對B之數量平均分子量的比率 <水溶性顆粒〇 β -¾狀糊精 (平均顆粒直徑20微米) γ-胺基丙基三乙氧基咬烧A1100 以矽烧偶合劑處理的β -環狀糊精 水溶性顆粒的份量(體積%) 〈鑄造條件〉 在從铸模移除之前的條件 後固化的條件 ί# 駟:·Χ3 105684.doc • 44. 1379853Ex. 8 (100%) (35.6%) (175.4) (4.84) 1 1 1 1 110〇C*30 minutes 110°C*16 hours Ex. 7 (100%) (35.6%) (175.4) (4.84) 240.8 1.204 CN (65.0%) 11(TC*30 minutes 110°C*16 hours Ex. 6 (100%) (35.6%) (175.4) (4.84) rn 0.006 rn (1.0%) 110〇C*30 minutes 110 °C*16 hours Ex. 5 (100%) (62.7%) (128.2) (17.94) 55.6 0.278 55.9 (30.0%) 110〇C*30 minutes 110°C*16 hours with a number average molecular weight of 300 or less The amount of the chain extender (% by weight) The amount of the trifunctional chain extender (% by weight) The number average molecular weight of the chain extender B The ratio of the number average molecular weight to the number average molecular weight of B < Water-soluble particles 〇β - 3⁄4-form dextrin (average particle diameter 20 μm) γ-aminopropyl triethoxy bite A1100 The amount of the water-soluble particles of β-cyclodextrin treated with the oxime coupling agent (% by volume) <Casting conditions> Conditions for curing after removal of conditions from the mold ί# 驷:·Χ3 105684.doc • 44. 1379853
«製)I崦«System" I崦
Ex. 4 in m ON in CN v〇 v〇 cs CN m oi 卜 Ex. 3 v〇 v〇 pH m s CN v〇 R 〇 in <N (N 00 rn 甘 CN Ex. 2 oo jn 1061 cn v〇 v〇 11.8 宕 CN m CN yr) Ex. 1 1895 o 10.8 17.2 v〇 S <N 2,136 硬度(Shore D) 在含浸於23°C去離子水之後24小時的硬度(Shore D) <儲存彈性係數E> 30°C E' 60°C E' 90°C E' 在30°C E·對60°C E'的比率 在30°C E’對90°C E'的比率 1磨表現的評估> 移除速率(毫微米/分鐘) 移除速率之晶圓内不均勻性(WIWNU) (%) 局部平坦化LSH (毫微米) 刮傷數/晶圓 i# 駟:yw 105684.doc -45- 1379853 (Ϊ) I<• ·Ex. 4 in m ON in CN v〇v〇cs CN m oi 卜Ex. 3 v〇v〇pH ms CN v〇R 〇in <N (N 00 rn 甘 CN Ex. 2 oo jn 1061 cn v〇 V〇11.8 宕CN m CN yr) Ex. 1 1895 o 10.8 17.2 v〇S <N 2,136 Hardness (Shore D) 24 hours after impregnation with 23 ° C deionized water (Shore D) <Storage elasticity Coefficient E> 30°CE' 60°CE' 90°CE' at 30°CE·to 60°C E' ratio at 30°C E' to 90°C E' ratio 1 grinding performance evaluation> In-wafer non-uniformity in addition to rate (nm/min) removal rate (WIWNU) (%) Localized flattening LSH (nm) Scratch number/wafer i# 驷:yw 105684.doc -45- 1379853 (Ϊ) I<• ·
Ex. 8 m v〇 (N VO ON On 00 cn CN uS OO 00 2,035 Ex. 7 g 1351 m in m CN in <N oo ^Τί <N v〇 cn r-H On m Ex. 6 CN VO 210 v〇 VO o CM (r5 uo 204 CS oi 00 un <N 00 Ex. 5 VO Os 00 <N S 236 <N cs VO 硬度(Shore D) 在含浸於23°c去離子水之後24小時的硬度(Shore D) <儲存彈性係數E'> 30。。E' 60°C E' 90°C E' 在30°C E'對60°C F的比率 在30°C E'對90°C E’的比率 1磨表現的評估> 移除速率(毫微米/分鐘) 移除速率之晶圓内不均勻性(WIWNU) (%) 局部平坦化LSH (毫微米) 刮傷數/晶圓 ¥駟:wa 105684.doc -46- 1379853 • · (憋饗)ϊ嵴 C. Ex. 2 (47.6%) (26.2%) (312.9) (1.52) 14.4 0.072 14.5 (10.0%) 110〇C*30 分鐘 110°C*16 小時 C. Ex. 1 (52.4%) (14.3%) (325.7) (1-46) 14.4 0.072 14.5 (10.0%) 110〇C*30 分鐘 110°C*16 小時 Ex. 10 (52.4%) (26.2%) (287.6) (1.66) 14.4 0.072 14.5 (10.0%) 110〇C*30 分鐘 110°C*16 小時 Ex. 9 (100%) 1_ (35.6%) (175.4) (4.84) 389.1 1.945 ON m (75.0%) 110。(:*30 分鐘 110°C*16 小時 具有數量平均分子量300或更少之鏈延伸劑的份量 (重量%) 三官能基鏈延伸劑的份量(重量%) 鏈延伸劑B的數量平均分子量 Y之數量平均分子量對B之數量平均分子量的比率 <水溶性顆粒c> β-琢·狀糊精 (平均顆粒直徑20微米) y-胺基丙基三乙氧基碎烧A1100 以矽烧偶合劑處理的β -環狀糊精 水溶性顆粒的份量(體積%) 〈鑄造條件〉 在從鑄模移除之前的條件 後固化的條件 ί4鎵 qi : ·Χ3 ϋ ί香駟:·Χ3 105684.doc -47- 1379853 (憋鷄)I嵴 C. Ex. 6 C. Ex. 5 (100%) (〇%) (267.2) 未知 1 1 1 1 10(TC*60 分鐘 100°C*16 小時 C. Ex. 4 (100%) (16.5%) (120.8) 未知 oi 1 1 (1.9%) 8(TC*20 分鐘 110°C*16 小時 C. Ex. 3 I (43.1%) (512.0) (0.49) 14.5 1 1 (10.0%) 80°C*20 分鐘 110°C*16 小時 具有數量平均分子量300或更少之鏈延伸劑的份量 (重量%) 三官能基鏈延伸劑的份量(重量°/〇) 鏈延伸劑B的數量平均分子量 Y之數量平均分子量對B之數量平均分子量的比率 <水溶性顆粒〇 β-環狀糊精 (平均顆粒直徑20微米) γ-胺基丙基三乙氧基石夕烧Α1100 以矽烧偶合劑處理的β -環狀糊精 水溶性顆粒的份量(體積%) 〈鑄造條件〉 在從鑄模移除之前的條件 後固化的條件 一4^^:·χ3·υ苳駟:.xw 105684.doc • 48· 1379853 (501 硌• · C.Ex.2 v〇 00 CN cn 18.7 29.9 v〇 11.2 00 v〇 CN CO CJEx. 1 ON VO v〇 425 oo 00 卜 v〇 CN v〇 uS <N v〇 1 < 6,874 Ex. 10 艺 1—H 724 00 vo VO 寸 11.0 217 VO (N s 384 Ex. 9 CN oo 1689 428 tn (N m Os <N in m (N O 2,123 石^^(Shore D) 在含浸於23°c去離子水之後24小時的硬度(Shore D) <儲存彈性係數E'> 30°C E' 60°C E' 90°C E' 在30°c E'對60°c E'的比率 在30°C E’對90°C E'的比率 磨表現的評估> 移除速率(毫微米/分鐘) 移除速率之晶圓内不均勻性(WIWNU) (%) 局部平坦化(毫微米) 刮傷數/晶圓 苳嚭qJLi: .χω·0 军駟:·Χ3 105684.doc • 49· 1379853 *饗)Ι<• · C.Ex.6 1_ cn 0 00 <N vq <N 00 ΓΛ v〇 (N CN v〇 00 m CN C. Ex. 5 CO 寸 〇\ in m 00 (N On R r A CN v〇 〇〇 〇\ 00 ΟΊ C. Ex. 4 m v〇 <N VO 274 m (N 00 cn in g CN cn Os C. Ex. 3 m 00 σ\ 1300 rn 100.0 118.2 13.5 00 ON o CN 硬度(Shore D) 在含浸於23°C去離子水之後24小時的硬度(Shore D) <儲存彈性係數E'> 30°C E' 60°C E' 90°C E' 在30°c E'對60°c E'的比率 在30°C E'對90°C E'的比率 ,磨表現的評估> 移除速率(毫微米/分鐘) 移除速率之晶圓内不均勻性(WTWNU) (%) 局部平坦化(毫微米) 刮傷數/晶圓 苳銻^: ·Χ3 ·3 i# 駟:·Χ3 105684.doc •50- 在比較例1中’其中在鏈延伸劑中之三官能基組份的含 1是低於20%,當儲存彈性係數隨溫度的改變為小、並且 緩和外來物質所產生之壓力的能力低時,大量的刮傷被產 生。比較例1之墊在平坦度上稍微差一點。在比較例2中, 其中在鏈延伸劑中具有數量平均分子量300或更低之組份 的含量是低於50重量❶/。’當儲存彈性係數隨溫度的改變為 大時’所得研磨墊在平坦度及平面上均勻度上較差。在比 較例3中’其中在鏈延伸劑中不包含具有數量平均分子量 300或更低的組份時’當聚胺基甲酸酯基質的相分離不完 全時’含浸在水中時的硬度改變是大的,並且有獲得墊之 真實使用的問題。在比較例4中,其中在鏈延伸劑中之三 官能基組份的含量是低於20%,當儲存彈性係數隨溫度的 改變為小、並且緩和外來物質所產生之壓力的能力低時, 大量的刮傷被產生。在比較例5中,其中在鏈延伸劑中不 包含三官能基組份’大量的刮傷被產生。在比較例6中, 其為商業可獲得之發泡聚胺基甲酸酯研磨墊,儲存彈性係 數隨溫度的改變為小’並且很大量的刮傷被產生。對照這 些,本發明之實例1至10的研磨墊具有良好的物理性質及 在性質之間的良好平衡。因此,這些研磨墊可優越地用來 研磨半導體晶圓或類似物。 105684.doc -51 -Ex. 8 mv〇(N VO ON On 00 cn CN uS OO 00 2,035 Ex. 7 g 1351 m in m CN in <N oo ^Τί <N v〇cn rH On m Ex. 6 CN VO 210 v〇 VO o CM (r5 uo 204 CS oi 00 un < N 00 Ex. 5 VO Os 00 < NS 236 < N cs VO hardness (Shore D) hardness after 24 hours of impregnation with 23 ° c deionized water ( Shore D) <Storage Elasticity E'> 30. E' 60°CE' 90°CE' at 30°C E' to 60°CF at 30°C E' to 90°C E' Evaluation of Ratio 1 Milling Performance> Removal Rate (nm/min) Wafer Inhomogeneity at Removal Rate (WIWNU) (%) Local Flattening LSH (Nano) Scratch Count/Fabric ¥驷: Wa 105684.doc -46- 1379853 • · (憋飨)ϊ嵴C. Ex. 2 (47.6%) (26.2%) (312.9) (1.52) 14.4 0.072 14.5 (10.0%) 110〇C*30 minutes 110° C*16 hours C. Ex. 1 (52.4%) (14.3%) (325.7) (1-46) 14.4 0.072 14.5 (10.0%) 110〇C*30 minutes 110°C*16 hours Ex. 10 (52.4% (26.2%) (287.6) (1.66) 14.4 0.072 14.5 (10.0%) 110〇C*30 minutes 110°C*16 hours Ex. 9 (100%) 1_ (35.6%) (175.4) (4.84) 389.1 1.945 ON m (75.0%) 110. (: * 30 minutes, 110 ° C * 16 hours, the amount of chain extender having a number average molecular weight of 300 or less (% by weight) The amount of the trifunctional chain extender (% by weight) The ratio of the number average molecular weight of the chain extender B to the number average molecular weight of B < water soluble particles c > β-琢·dextrin (average particle diameter 20 μm) y-aminopropyl triethyl Alkyl calcination A1100 The amount (% by volume) of water-soluble granules of β-cyclodextrin treated with a smouldering coupler <Casting conditions> Conditions for curing after conditions removed from the mold ί4 Gallium qi : ·Χ3 ϋ ί香驷:·Χ3 105684.doc -47- 1379853 (憋鸡)I嵴C. Ex. 6 C. Ex. 5 (100%) (〇%) (267.2) Unknown 1 1 1 1 10 (TC*60 Minute 100°C*16 hours C. Ex. 4 (100%) (16.5%) (120.8) Unknown oi 1 1 (1.9%) 8 (TC*20 minutes 110°C*16 hours C. Ex. 3 I ( 43.1%) (512.0) (0.49) 14.5 1 1 (10.0%) 80°C*20 minutes 110°C*16 hours Part of the chain extender with a number average molecular weight of 300 or less (% by weight) Trifunctional chain Delay The amount of the agent (weight ° / 〇) The ratio of the number average molecular weight Y of the chain extender B to the number average molecular weight of B < water-soluble particles 〇β-cyclodextrin (average particle diameter 20 μm) γ -Aminopropyltriethoxy saponin 1100 The amount of the water-soluble granules of the β-cyclodextrin treated with the oxime coupling agent (% by volume) <Casting conditions> Conditions for curing after the conditions before removal from the mold A 4^^:·χ3·υ苳驷:.xw 105684.doc • 48· 1379853 (501 硌• · C.Ex.2 v〇00 CN cn 18.7 29.9 v〇11.2 00 v〇CN CO CJEx. 1 ON VO v〇425 oo 00 卜v〇CN v〇uS <N v〇1 < 6,874 Ex. 10 Art 1—H 724 00 vo VO inch 11.0 217 VO (N s 384 Ex. 9 CN oo 1689 428 tn ( N m Os <N in m (NO 2,123 Stone^^(Shore D) Hardness after 24 hours of impregnation with 23°c deionized water (Shore D) <Storage Elasticity E'> 30°CE' 60 °CE' 90°CE' at 30°c E' vs. 60°c E' ratio at 30°C E' vs. 90°C E' ratio mill performance evaluation> Removal rate (nm/min) Remove rate of wafer Inhomogeneity (WIWNU) (%) Local flattening (nano) Scratch number/wafer 苳嚭qJLi: .χω·0 Military 驷:·Χ3 105684.doc • 49· 1379853 *飨)Ι<• · C .Ex.6 1_ cn 0 00 <N vq <N 00 ΓΛ v〇(N CN v〇00 m CN C. Ex. 5 CO 〇 〇\ in m 00 (N On R r A CN v〇〇〇 〇\ 00 ΟΊ C. Ex. 4 mv〇<N VO 274 m (N 00 cn in g CN cn Os C. Ex. 3 m 00 σ\ 1300 rn 100.0 118.2 13.5 00 ON o CN Hardness (Shore D) Hardness 24 Hours after impregnation with 23 ° C deionized water (Shore D) <Storage Elasticity E'> 30°CE' 60°CE' 90°CE' at 30°C E' vs. 60°c E' Ratio at 30 ° C E' to 90 ° C E ' ratio, evaluation of grinding performance > removal rate (nm / min) removal rate of wafer inhomogeneity (WTWNU) (%) local flatness (nano) scratch number/wafer 苳锑^: ·Χ3 ·3 i# 驷:·Χ3 105684.doc •50- In Comparative Example 1, 'the trifunctional component of the chain extender Containing 1 is less than 20%, when the storage elastic modulus changes with temperature is small, and the pressure generated by foreign substances is alleviated Low capacity, a large number of scratches are produced. The pad of Comparative Example 1 was slightly worse in flatness. In Comparative Example 2, the content of the component having a number average molecular weight of 300 or less in the chain extender was less than 50% by weight. When the storage elastic modulus changes with temperature, the resulting polishing pad is inferior in flatness and uniformity in plane. In Comparative Example 3, 'When the component having a number average molecular weight of 300 or less is not contained in the chain extender, 'when the phase separation of the polyurethane matrix is incomplete, the hardness change when impregnated in water is Big, and there is the problem of getting the real use of the pad. In Comparative Example 4, wherein the content of the trifunctional component in the chain extender is less than 20%, when the change in the storage elastic modulus with temperature is small, and the ability to moderate the pressure generated by the foreign substance is low, A large number of scratches were produced. In Comparative Example 5, in which a trifunctional component was not contained in the chain extender, a large amount of scratch was produced. In Comparative Example 6, which is a commercially available foamed polyurethane polishing pad, the storage elastic coefficient was small with temperature change and a large amount of scratch was generated. In contrast to these, the polishing pads of Examples 1 to 10 of the present invention have good physical properties and a good balance between properties. Therefore, these polishing pads can be advantageously used to polish semiconductor wafers or the like. 105684.doc -51 -
Claims (1)
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JP2004299522A JP4475404B2 (en) | 2004-10-14 | 2004-10-14 | Polishing pad |
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TW200631999A TW200631999A (en) | 2006-09-16 |
TWI379853B true TWI379853B (en) | 2012-12-21 |
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TW094136056A TWI379853B (en) | 2004-10-14 | 2005-10-14 | Polishing pad |
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US (1) | US7217179B2 (en) |
EP (1) | EP1647359B1 (en) |
JP (1) | JP4475404B2 (en) |
KR (1) | KR101189349B1 (en) |
CN (1) | CN1760240B (en) |
DE (1) | DE602005004220T2 (en) |
TW (1) | TWI379853B (en) |
Families Citing this family (58)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI385050B (en) * | 2005-02-18 | 2013-02-11 | Nexplanar Corp | Customized polishing pads for cmp and methods of fabrication and use thereof |
JP5193595B2 (en) * | 2005-09-22 | 2013-05-08 | 株式会社クラレ | Polymer material, foam obtained therefrom and polishing pad using the same |
US20070161720A1 (en) * | 2005-11-30 | 2007-07-12 | Applied Materials, Inc. | Polishing Pad with Surface Roughness |
JP4926548B2 (en) * | 2006-06-09 | 2012-05-09 | 株式会社クラレ | Manufacturing method of polarizing film |
US7371160B1 (en) | 2006-12-21 | 2008-05-13 | Rohm And Haas Electronic Materials Cmp Holdings Inc. | Elastomer-modified chemical mechanical polishing pad |
US7438636B2 (en) * | 2006-12-21 | 2008-10-21 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Chemical mechanical polishing pad |
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KR101137975B1 (en) | 2007-05-10 | 2012-04-20 | 히다치 막셀 에너지 가부시키가이샤 | Method for production of electrochemical element |
JP5072442B2 (en) * | 2007-06-07 | 2012-11-14 | 富士紡ホールディングス株式会社 | Polishing pad manufacturing method and polishing pad |
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US20090062414A1 (en) * | 2007-08-28 | 2009-03-05 | David Picheng Huang | System and method for producing damping polyurethane CMP pads |
TWI455795B (en) * | 2007-10-18 | 2014-10-11 | Iv Technologies Co Ltd | Polishing pad and polishing method |
CN101422882B (en) * | 2007-10-31 | 2015-05-20 | 智胜科技股份有限公司 | Grinding mat and method |
US8052507B2 (en) * | 2007-11-20 | 2011-11-08 | Praxair Technology, Inc. | Damping polyurethane CMP pads with microfillers |
US8388799B2 (en) | 2008-01-24 | 2013-03-05 | Jsr Corporation | Composition for forming polishing layer of chemical mechanical polishing pad, chemical mechanical polishing pad and chemical mechanical polishing method |
JP5549111B2 (en) * | 2008-05-22 | 2014-07-16 | Jsr株式会社 | Composition for forming polishing layer of chemical mechanical polishing pad, chemical mechanical polishing pad, and chemical mechanical polishing method |
US20100035529A1 (en) * | 2008-08-05 | 2010-02-11 | Mary Jo Kulp | Chemical mechanical polishing pad |
IL196146A (en) | 2008-12-23 | 2014-01-30 | Elta Systems Ltd | System and method of transmitting a signal back towards a transmitting source |
JP5393434B2 (en) * | 2008-12-26 | 2014-01-22 | 東洋ゴム工業株式会社 | Polishing pad and manufacturing method thereof |
US8303375B2 (en) | 2009-01-12 | 2012-11-06 | Novaplanar Technology, Inc. | Polishing pads for chemical mechanical planarization and/or other polishing methods |
US9056382B2 (en) | 2009-05-27 | 2015-06-16 | Rogers Corporation | Polishing pad, composition for the manufacture thereof, and method of making and using |
JP4636347B1 (en) * | 2009-06-29 | 2011-02-23 | Dic株式会社 | Two-component urethane resin composition for polishing pad, polyurethane polishing pad, and method for producing polyurethane polishing pad |
US8697239B2 (en) * | 2009-07-24 | 2014-04-15 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Multi-functional polishing pad |
EP2517828A1 (en) * | 2009-12-22 | 2012-10-31 | JSR Corporation | Pad for chemical mechanical polishing and method of chemical mechanical polishing using same |
CN101892014A (en) * | 2010-08-24 | 2010-11-24 | 青岛沙木国际贸易有限公司 | Elastic grinding material for sandblasting treatment |
SG189457A1 (en) | 2010-10-26 | 2013-05-31 | Toyo Tire & Rubber Co | Polishing pad and method for producing same |
WO2012056513A1 (en) | 2010-10-26 | 2012-05-03 | 東洋ゴム工業株式会社 | Polishing pad and method for producing same |
TWI568541B (en) * | 2010-12-22 | 2017-02-01 | Jsr Corp | Chemical mechanical grinding method |
JP5404673B2 (en) * | 2011-02-25 | 2014-02-05 | 株式会社東芝 | CMP apparatus, polishing pad, and CMP method |
JP5875300B2 (en) * | 2011-09-06 | 2016-03-02 | 東洋ゴム工業株式会社 | Polishing pad and manufacturing method thereof |
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US8512427B2 (en) * | 2011-09-29 | 2013-08-20 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Acrylate polyurethane chemical mechanical polishing layer |
JP5528648B1 (en) * | 2012-09-10 | 2014-06-25 | 住友精化株式会社 | Polishing aid and abrasive composition containing the polishing aid |
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JP5661130B2 (en) * | 2013-01-31 | 2015-01-28 | 東洋ゴム工業株式会社 | Polishing pad |
US20140256231A1 (en) * | 2013-03-07 | 2014-09-11 | Dow Global Technologies Llc | Multilayer Chemical Mechanical Polishing Pad With Broad Spectrum, Endpoint Detection Window |
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US9233451B2 (en) | 2013-05-31 | 2016-01-12 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Soft and conditionable chemical mechanical polishing pad stack |
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US9238296B2 (en) | 2013-05-31 | 2016-01-19 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Multilayer chemical mechanical polishing pad stack with soft and conditionable polishing layer |
CN103878707B (en) * | 2014-03-31 | 2016-04-13 | 湖北鼎龙化学股份有限公司 | Polishing pad of chemically mechanical polishing and preparation method thereof |
US20150306731A1 (en) | 2014-04-25 | 2015-10-29 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Chemical mechanical polishing pad |
US9586304B2 (en) * | 2014-12-19 | 2017-03-07 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Controlled-expansion CMP PAD casting method |
EP3352944B1 (en) * | 2015-09-25 | 2022-10-26 | CMC Materials, Inc. | Polyurethane cmp pads having a high modulus ratio |
JP6761566B2 (en) * | 2015-10-02 | 2020-09-30 | 富士紡ホールディングス株式会社 | Abrasive pad |
JP6691658B2 (en) * | 2015-10-02 | 2020-05-13 | 富士紡ホールディングス株式会社 | Polishing pad |
US9484212B1 (en) | 2015-10-30 | 2016-11-01 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Chemical mechanical polishing method |
CN106041719B (en) * | 2016-06-03 | 2018-10-23 | 湖北鼎龙控股股份有限公司 | A kind of polishing layer and preparation method thereof and chemical mechanical polishing pads |
US10086494B2 (en) * | 2016-09-13 | 2018-10-02 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | High planarization efficiency chemical mechanical polishing pads and methods of making |
JP6732382B2 (en) * | 2016-10-12 | 2020-07-29 | 株式会社ディスコ | Processing device and method of processing workpiece |
KR101949905B1 (en) * | 2017-08-23 | 2019-02-19 | 에스케이씨 주식회사 | Porous polyurethane polishing pad and preparation method thereof |
US10464187B2 (en) * | 2017-12-01 | 2019-11-05 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | High removal rate chemical mechanical polishing pads from amine initiated polyol containing curatives |
CN109824854B (en) * | 2018-12-27 | 2021-09-28 | 湖北鼎汇微电子材料有限公司 | Polishing pad |
JP7331453B2 (en) * | 2019-05-17 | 2023-08-23 | Dic株式会社 | Method for manufacturing porous body |
US20210122007A1 (en) * | 2019-10-23 | 2021-04-29 | Skc Co., Ltd. | Composition for polishing pad and polishing pad |
KR102287235B1 (en) * | 2019-10-30 | 2021-08-06 | 에스케이씨솔믹스 주식회사 | Polishing pad with controlled crosslinking and preparation method thereof |
CN110877287A (en) * | 2019-12-10 | 2020-03-13 | 上海华力微电子有限公司 | Grinding system |
CN117024701B (en) * | 2023-08-14 | 2024-04-09 | 旭川化学(苏州)有限公司 | Polyurethane foaming polishing material and preparation method and application thereof |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MY114512A (en) | 1992-08-19 | 2002-11-30 | Rodel Inc | Polymeric substrate with polymeric microelements |
US6022268A (en) | 1998-04-03 | 2000-02-08 | Rodel Holdings Inc. | Polishing pads and methods relating thereto |
JP3668046B2 (en) | 1998-05-11 | 2005-07-06 | 株式会社東芝 | Polishing cloth and method for manufacturing semiconductor device using the polishing cloth |
US6337280B1 (en) | 1998-05-11 | 2002-01-08 | Kabushiki Kaisha Toshiba | Polishing cloth and method of manufacturing semiconductor device using the same |
JP3918359B2 (en) | 1998-05-15 | 2007-05-23 | Jsr株式会社 | Polymer composition for polishing pad and polishing pad |
JP2002535843A (en) * | 1999-01-21 | 2002-10-22 | ロデール ホールディングス インコーポレイテッド | Improved polishing pad and associated method |
US6454634B1 (en) * | 2000-05-27 | 2002-09-24 | Rodel Holdings Inc. | Polishing pads for chemical mechanical planarization |
JP3925041B2 (en) | 2000-05-31 | 2007-06-06 | Jsr株式会社 | Polishing pad composition and polishing pad using the same |
JP2002137160A (en) | 2000-08-24 | 2002-05-14 | Toray Ind Inc | Pad for polishing, polishing device, and polishing method |
US6706383B1 (en) * | 2001-11-27 | 2004-03-16 | Psiloquest, Inc. | Polishing pad support that improves polishing performance and longevity |
KR100857504B1 (en) * | 2000-12-01 | 2008-09-08 | 도요 고무 고교 가부시키가이샤 | Cushion layer for polishing pad |
EP1354913B1 (en) * | 2000-12-08 | 2016-10-26 | Kuraray Co., Ltd. | Thermoplastic polyurethane foam, process for production thereof and polishing pads made of the foam |
JP2003064143A (en) | 2001-08-23 | 2003-03-05 | Showa Denko Kk | Urethane molded product for polishing pad and the polishing pad |
KR100845481B1 (en) * | 2001-11-13 | 2008-07-10 | 도요 고무 고교 가부시키가이샤 | Grinding pad and method of producing the same |
-
2004
- 2004-10-14 JP JP2004299522A patent/JP4475404B2/en not_active Expired - Fee Related
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2005
- 2005-10-11 US US11/246,199 patent/US7217179B2/en active Active
- 2005-10-11 DE DE602005004220T patent/DE602005004220T2/en active Active
- 2005-10-11 EP EP05022097A patent/EP1647359B1/en not_active Expired - Fee Related
- 2005-10-13 KR KR1020050096583A patent/KR101189349B1/en not_active IP Right Cessation
- 2005-10-14 CN CN2005101199865A patent/CN1760240B/en not_active Expired - Fee Related
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US20060084365A1 (en) | 2006-04-20 |
DE602005004220T2 (en) | 2009-01-08 |
US7217179B2 (en) | 2007-05-15 |
JP4475404B2 (en) | 2010-06-09 |
JP2006111700A (en) | 2006-04-27 |
KR101189349B1 (en) | 2012-10-09 |
DE602005004220D1 (en) | 2008-02-21 |
EP1647359A1 (en) | 2006-04-19 |
CN1760240A (en) | 2006-04-19 |
EP1647359B1 (en) | 2008-01-09 |
KR20060053261A (en) | 2006-05-19 |
TW200631999A (en) | 2006-09-16 |
CN1760240B (en) | 2010-06-16 |
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